Metal-organic frameworks as ion capture compositions

ABSTRACT

Embodiments of the present disclosure pertain to methods of capturing one or more ions from an environment by associating the environment with a composition that includes a metal-organic framework. The association results in the capture of the one or more ions by the metal-organic framework. The metal-organic frameworks may include a plurality of metals and a plurality of triphenylene-based ligands that interconnect the plurality of the metals. The methods of the present disclosure may also include a step of detecting one or more captured ions. Additional embodiments of the present disclosure pertain to the compositions for capturing one or more ions from an environment.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 16/636,081, filed on Feb. 3, 2020, which is a U.S.national stage application of International Patent Application No.PCT/US2018/046510, filed on Aug. 13, 2018, which claims priority to U.S.Provisional Patent Application No. 62/544,355, filed on Aug. 11, 2017.The entirety of each of the aforementioned applications is incorporatedherein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with government support under W911NF-17-1-0398awarded by the Department of Defense. The government has certain rightsin the invention.

BACKGROUND

Current methods and compositions for capturing ions from variousenvironments suffer from numerous limitations, such as limitedadsorption capacity, limited ion selectivity, limited adsorptionkinetics, non-reusability, and lack of multifunctionality. Variousembodiments of the present disclosure address the aforementionedlimitations.

SUMMARY

In some embodiments, the present disclosure pertains to methods ofcapturing one or more ions from an environment by associating theenvironment with a composition that includes a metal-organic framework.The associating results in the capture of the one or more ions by themetal-organic framework.

In some embodiments, the metal-organic framework is in the form of amulti-layered and stacked structure. In some embodiments, themetal-organic framework is in the form of a two-dimensional conductivenetwork. In some embodiments, the metal-organic framework is incrystalline form.

In some embodiments, the metal-organic framework includes a plurality ofmetals and a plurality of aromatic (e.g., triphenylene-based) ligandsthat interconnect the plurality of the metals. In some embodiments, theplurality of the triphenylene-based ligands include, without limitation,hexatopic triphenylene-based ligands,2,3,5,6,10,11-hexahydroxytriphenylene (HHTP),2,3,5,6,10,11-hexaiminotriphenylene (HITP),2,3,5,6,10,11-hexathiotriphenylene (HTTP), and combinations thereof.

In some embodiments, a plurality of functional groups in themetal-organic framework are appended to a plurality of aromatic ligands.In some embodiments, the plurality of functional groups include, withoutlimitation, hydroxy groups, amine groups, thiol groups, coordinatedgroups thereof, deprotonated groups therefore, and combinations thereof.

In some embodiments, the metal-organic framework includes, withoutlimitation, Ni₃(HHTP)₂, Ni₃(HITP)₂, CU₃(HHTP)₂, Cu₃(HITP)₂, andcombinations thereof. In some embodiments, the metal-organic frameworkincludes Ni₃(HITP)₂.

In some embodiments, the methods of the present disclosure also includea step of detecting one or more captured ions. In some embodiments, thedetecting includes detecting a change in potential of the metal-organicframework and correlating the change in the potential to the presence ofthe one or more ions. In some embodiments, the detection includesdetecting a change in current passing through the metal-organicframework.

Additional embodiments of the present disclosure pertain to thecompositions of the present disclosure for capturing one or more ionsfrom an environment. In some embodiments, the compositions of thepresent disclosure are in the form of a membrane.

DESCRIPTION OF THE DRAWINGS

FIG. 1A depicts an ion-selective electrode.

FIG. 1B illustrates a method of detecting an ion in a sample.

FIG. 1C illustrates a method of forming an ion-selective electrode.

FIG. 1D illustrates a method of capturing ions from a sample.

FIG. 2 provides a schematic representation of the layered devicearchitecture employed in Example 1. A thin film of metal-organicframework (MOF) is drop casted directly on the top of a glassy carbonelectrode (GCE), and then covered with an ion-selective membrane (ISM)to facilitate potentiometric ion sensing.

FIG. 3A-3C show scanning electron microscopy (SEM) results andaccompanied energy dispersive X-ray spectroscopy (EDX) analysiscollected for different metal-organic frameworks (MOFs), includingCu₃HHTP₂ MOF (FIG. 3A), Ni₃HHTP₂ MOF (FIG. 3B), and Co₃HHTP₂ MOF (FIG.3C). SEM revealed the assembly of M₃HHTP₂ conductive MOFs intonanocrystalline structures while EDX confirmed the presence oforganic-inorganic hybrid materials as reported for other HHTP basedMOFs.

FIG. 4 shows experimental (colored) and simulated slipped parallelpowder X-Ray Diffraction patterns without the presence of interpolatedlayer obtained for bulk Cu₃HHTP₂, Ni₃HHTP₂ and Co₃HHTP₂ MOFs. Theobserved pXRD patterns of Cu₃HHTP₂, Ni₃HHTP₂, and Co₃HHTP₂ MOF areconsistent with previous reports.

FIGS. 5A-5C show X-ray photoelectron spectroscopy (XPS) spectra obtainedfor the Co₃HHTP₂ MOFs. FIG. 5A is an energy survey scan. Also shown arehigh-resolution spectra in the O1s (FIG. 5B), and Co2p3 (FIG. 5C)regions.

FIGS. 6A-6C show XPS spectra obtained for the Ni₃HHTP₂ MOFs. FIG. 6A isan energy survey scan. Also shown are high-resolution spectra in the O1s(FIG. 6B), and Ni2p3 (FIG. 6C) regions.

FIGS. 7A-7C show XPS spectra obtained for the Cu₃HHTP₂ MOFs. FIG. 7A isan energy survey scan. Also shown are high-resolution spectra in the O1s(FIG. 7B), and Cu2p3 (FIG. 7C) regions.

FIGS. 8A-8B show various spectra for different ion-selective electrodes.FIG. 8A shows electrochemical impedance spectroscopy (EIS) spectraobtained for a drop-cast layer of either Co₃HHTP₂, Ni₃HHTP₂, or Cu₃HHTP₂MOFs deposited on glassy carbon electrodes. FIG. 8B shows impedancespectra obtained for the glassy carbon electrodes (GCE) coated withdifferent thicknesses of drop cast Ni₃HHTP₂ layers: 20±8 μm (redtriangles), 40±5 μm (blue circles), and 60±5 μm (black squares). Insetshows a zoomed-in representation of the high frequency impedance data(100 kHz-3 Hz). Inset shows a zoomed-in representation of the highfrequency impedance data (100 kHz-3 Hz). In both cases (FIGS. 8A and8B), the proposed equivalent circuit includes the resistance of thesolution (R1), charge transfer resistance (R2), and two constant phaseelements (CPE1 and CPE2). Frequency range: 100 kHz-10 mHz; amplitudepotential: 0.01 V; solution: 0.1 M KCl.

FIGS. 9A-9C show interferometer data for the GCE/M₃HHTP₂ MOF (M=Co, Ni,Co) electrodes prepared by drop casting 10 μL of Ni₃HHTP₂-MOF suspension(1 mg/mL) onto a surface of glassy carbon electrodes. The difference inheight between the blue and red regions were used to calculate thicknessof the MOF layer.

FIGS. 10A-10C show interferometer data for the GCE/MOF electrodesprepared by drop casting 2 μL (FIG. 10A), 5 μL (FIG. 10B) and 10 μL(FIG. 10C) of Ni₃HHTP₂-MOF suspension (1 mg/mL) onto a surface of glassycarbon electrodes. The difference in height between the blue and redregions were used to calculate the thickness of the MOF layer.

FIGS. 11A-11C show cyclic voltammograms obtained for glassy carbonelectrodes coated with 60 μm layers of Ni₃HHTP₂ (FIG. 11A), Co₃HHTP₂(FIG. 11B), and Cu₃HHTP₂ (FIG. 11C) MOFs. Experimental parameters—scanrate: 50 mV/sec, background electrolyte: 0.1 M KCl and scanning range:−0.5 V to 0.5 V. The arrow indicates scan direction.

FIG. 12 shows on the left panel impedance spectrum obtained for glassycarbon electrodes at three different applied potenitals (0.0 V—bluecircles; 0.3 V—black squares; and −0.3 V red triangles) with drop castNi₃HHTP₂ MOF layer (2 μL aliquot of MOF solution-20 μm thickness). Theright panel shows a zoomed in representation of the high frequencyimpedance data for the same electrode configuration (100 kHz-3 Hz). Nosignificant difference in response characteristics was obsereved for thestudied electrodes. This demonstrates that the total capacitance of thesystem is independent of the faradic process observed during cyclicvoltammetry measurements. Frequency range: 100 kHz-10 mHz; amplitudepotential: 0.01 V; solution: 0.1 M KCl.

FIGS. 13A-13B show the impedance spectra of potassium ion-selectivemembranes (K⁺-ISM-II) deposited onto bare glassy carbon electrode (FIG.13A) and the same K⁺ ISM-II deposited on top of Ni₃HHTP₂ MOF/GCEsubstrate (FIG. 13B). Inset demonstrates zoomed in impedance response athigh frequency spectral region. The equivalent circuits used for fittingimpedance data are shown in the top right corner of each presentedspectrum. Frequency range: 100 kHz-10 mHz; amplitude potential: 0.1 V;solution: 0.1 M KCl.

FIG. 14 shows chronopotentiograms obtained during the analysis ofK⁺-ISM-II based ion-selective electrodes (ISEs) under polarizingconditions. The top panel shows K⁺-ISM-II applied directly onto a GCEcontact without the MOF as undelaying conductive layer. The bottom panelshows a GCE/Ni₃HHTP₂ MOF/K⁺-ISM-II electrode. The inset demonstrates aclose-up of response obtained for the GCE/Ni₃HHTP₂ MOF/K⁺-ISM-II.Experimental conditions: applied current +1 nA for 60 seconds followedby −1 nA for 60 seconds. Background solution was 0.1 M KCl.

FIGS. 15A-15B show a potentiometric response of GCE/MOF/ISM devices tomodel anions and cations. In this electrode configuration, the Ni₃HHTP₂MOF was drop-cast directly onto the glassy carbon electrode and then theresulting conductive layer was covered with either NO₃ ⁻-ISM (redsquares) (FIG. 15A), K⁺-ISM-I (blue diamonds) (FIG. 15B), and K⁺-ISM-II(green triangles) (FIG. 15B) selective polymeric membrane. For theK⁺-ISM-I electrodes a near-Nernstian slope of 58.2±1.0 mV decade⁻¹ and ananomolar limit of detection (LODs) of 5.01±0.01×10⁻⁷ M was observed.The K⁺-ISM-II exhibited a near-Nernstian slope of 54.1±1.0 mV decade⁻¹with LODs found at 6.76±0.03×10⁻⁶ M, while 56.3±0.5 mV decade⁻¹ slopewith LODs of 6.31±0.01×10⁻⁷ M was obtained for NO₃ ⁻-ISM electrodes.

FIG. 16 shows potentiometric responses of glassy carbon electrodescoated with Ni₃HHTP₂ and then covered with the NO₃ ⁻-ISM for variouscations: Cl⁻ (green diamonds), NO₃ ⁻ (red squares), BP (black triangles)and SO₄ ²⁻ (grey circles).

FIG. 17 shows short term stability of GCE/MOF/NO₃ ⁻-ISM immersed in1.0×10⁻³ M NH₄NO₃. Good potential stability with minimal drift wasrecorded for the electrodes with Ni₃HHTP₂ used as ion-to-electrontransducer. The electrodes were prepared according to the protocolsdescribed in the Experimental section.

FIG. 18 shows long term stability of GCE/M₀F/NO₃ ⁻ ISM electrodesimmersed in 1.0×10⁻³ M NH₄NO₃. Minimal change in standard potential (˜10mV±3) was recorded for the electrodes with Ni₃HHTP₂ used asion-to-electron transducers. The electrodes were stored in ultra-purewater for 25 days prior to the potentiometric experiments. Thedeterioration in the detection limits of these electrodes could beattributed to leaching of membrane components from the polymeric matrixinto the sample solution during storage. The electrodes were preparedaccording to the protocols described in the Experimental section.

FIG. 19 shows light stability of GCE/MOF/K⁺-ISM-II electrodes immersedin 1.0×10⁻³ M KCl. Minimal potential drift was observed for theelectrodes with Ni₃HHTP₂ used as ion-to-electron transducers uponswitching the room lights on and off.

FIG. 20 shows experimental (colored) and simulated slipped parallelpowder X-Ray diffraction patterns without the presence of interpolatedlayer obtained for Cu₃HHTP₂, Ni₃HHTP₂ and Co₃HHTP₂ MOFs afterpotentiometric measurements with K⁺-ISM-II electrodes. The observed pXRDpatterns of Cu₃HHTP₂, Ni₃HHTP₂, and Co₃HHTP₂ MOFs matched those of bulkpowder and are consistent with previous reports. These findings indicatethat the crystallinity of the MOF is retained both during and afteranalytical measurements.

FIGS. 21A-21C show potentiometric responses of M₃HHTP₂ based ISE forK⁺-ISM-II. In this electrode configuration, either 10 μL of Ni₃HHTP₂(FIG. 21A), Co₃HHTP₂ (FIG. 21B) or Cu₃HHTP₂ (FIG. 21C) suspensions weredrop cast directly onto the glassy carbon electrode and then theresulting conductive layer was covered with potassium selectivepolymeric membrane (10 μL of the K⁺-ISM-II membrane solution asdescribed in the ‘Preparation of K⁺ and NO₃ ⁻ sensing membranes’). Theslopes obtained for the Ni₃HHTP₂ MOF/K⁺-ISM-II, Co₃HHTP₂ MOF/K⁺-ISM-II,and Cu₃HHTP₂ MOF/K⁺-ISM-II were 55.1±1.2 mV/decade, 56.2±1.0 mV/decadeand 52.6±2.1 mV/decade, respectively.

FIG. 22 shows potentiometric responses of glassy carbon electrodescoated with Ni₃HHTP₂ and then covered with the K⁺-ISM-II for variouscations: K⁺ (blue circles), NH₄ ⁺ (green diamonds), Na⁺ (blacktriangles) and Ca²⁺ (grey squares).

FIG. 23 shows potentiometric responses of glassy carbon electrodescoated with Ni₃HHTP₂ and then covered with the K⁺-ISM-I for variouscations: K⁺ (blue circles), NH₄ ⁺ (green diamonds), Na (black triangles)and Ca²⁺ (grey squares).

FIGS. 24A-24B show the results of water layer tests. FIG. 24A showswater film tests of solid-contact K⁺-ISM-II electrodes based on theGCE/MOF/K⁺-ISM-II configuration. At t=1 h, the primary ion solution (0.1M KCl) was exchanged to 0.1 M NaCl, and after 3 h, the sample wasreplaced by the initial solution for 8 h. FIG. 24B shows thepotentiometric water layer test of GCE/MOF/NO₃ ⁻-ISM electrodes. At t=1h, the primary analyte solution (0.1 M NH₄NO₃) was exchanged to 0.1 MCaCl₂, and after 3 h, the sample was replaced by the initial solutionfor 8 h.

FIG. 25 shows a contact angle image of 2 μL of water placed on top of aNi₃HHTP₂ coated glassy carbon electrode (GCE/Ni₃HHTP₂ MOF).

FIG. 26 shows a schematic representation of the experimental devicearchitecture employed in Example 2. The conductive MOF powder iscompressed directly on the surface of a gold electrode and then used forpotentiometric ion sensing without any sample or electrode pretreatment.

FIG. 27 shows potentiometric responses recorded for Ni₃HHTP₂ andCu₃HHTP₂ MOFs for Na⁺ and Cl⁻ ions. Cu₃HHTP₂ MOF in the form of pressedelectrodes exhibited cationic responses to Nat, while Ni₃HHTP₂ respondedpreferentially to anionic species (Cl⁻).

FIG. 28 shows the potentiometric response of Cu₃HHTP₂ pressed electrodesto copper (II) ions. The inset demonstrates a linear response range ofthe same electrode.

FIG. 29 shows the potentiometric response of pressed Ni₃HHTP₂ MOFelectrodes for chloride ions. At high concentrations of Cl⁻, theelectrode stops responding to anions. Upon further addition of NaCl, thecationic type of response is observed.

FIG. 30 shows the light stability of Cu₃HHTP₂ MOF electrodes immersed in10 mM CuSO₄. Minimal potential drift was observed for the pressedelectrodes upon switching the room lights on and off.

FIG. 31 shows the light stability of Cu₃HHTP₂ MOFs electrodes immersedin 10 mM CuSO₄. Minimal potential drift was observed for the pressedelectrodes upon switching the room lights on and off.

FIG. 32 shows the bottom-up synthesis of M₃HHTP₂ MOFs from HHTP andmetal salts.

FIGS. 33A-33C show SEM results and accompanied EDX analyses collectedfor Cu₃(HHTP)₂ MOF (FIG. 33A), Ni₃(HHTP)₂ MOF (FIG. 33B), and Co₃(HHTP)₂MOF (FIG. 33C).

FIG. 34 illustrates an experimental set up for a MOF-based ion capturemembrane.

FIG. 35 provides simulated and experimental PXRD patterns of Cu₃(HHTP)₂,Cu₃(HITP)₂, Ni₃(HITP)₂ and Ni₃(HHTP)₂ MOFs.

FIGS. 36A-36D provide depictions of the structures of Ni₃(HHTP)₂ (FIG.36A), Ni₃(HITP)₂ (FIG. 36B), Cu₃(HHTP)₂ (FIG. 36C), and Cu₃(HITP)₂ (FIG.36D) MOFs.

FIGS. 37A-37D provide SEM images of Ni₃(HHTP)₂ (FIG. 37A), Ni₃(HITP)₂(FIG. 37B), Cu₃(HHTP)₂ (FIG. 37C), and Cu₃(HITP)₂ (FIG. 37D) MOFs.

FIGS. 38A-38B provide experimental results of the capture of dichromate(Cr₂O₇)²⁻ (FIG. 38A) and Permanganate (MnO₄)— (FIG. 38B) by variousMOFs.

FIGS. 39A-39B illustrate the concentration dependent ion capture ofdichromate (FIG. 39A) and permanganate (FIG. 39B) ions by Ni₃(HITP)₂MOFs.

FIGS. 40A-40B illustrate time dependent ion capture of dichromate (FIG.40A) and permanganate (FIG. 40B) ions by Ni₃(HITP)₂ MOFs.

FIGS. 41A-41B illustrate time dependent ion capture of dichromate (FIG.41A) and permanganate (FIG. 41B) ions by Ni₃(HITP)₂ MOFs.

FIGS. 42A-42B show post ion-capture characterization of Ni₃(HITP)₂ MOFsby pXRD after the capture of dichromate (FIG. 42A) and permanganate(FIG. 42B) ions.

FIG. 43 illustrates the potentiometric sensing of KMnO₄ with Ni₃(HITP)₂.

DETAILED DESCRIPTION

It is to be understood that both the foregoing general description andthe following detailed description are illustrative and explanatory, andare not restrictive of the subject matter, as claimed. In thisapplication, the use of the singular includes the plural, the word “a”or “an” means “at least one”, and the use of “or” means “and/or”, unlessspecifically stated otherwise. Furthermore, the use of the term“including”, as well as other forms, such as “includes” and “included”,is not limiting. Also, terms such as “element” or “component” encompassboth elements or components that includes one unit and elements orcomponents that include more than one unit unless specifically statedotherwise.

The section headings used herein are for organizational purposes and arenot to be construed as limiting the subject matter described. Alldocuments, or portions of documents, cited in this application,including, but not limited to, patents, patent applications, articles,books, and treatises, are hereby expressly incorporated herein byreference in their entirety for any purpose. In the event that one ormore of the incorporated literature and similar materials defines a termin a manner that contradicts the definition of that term in thisapplication, this application controls.

Potentiometric sensors are an important class of analytical devices withbroad utility in clinical and environmental analysis. Driven by theprogress at the interfaces of analytical, supramolecular, and materialschemistry, modern potentiometric devices have evolved from mechanicallyfragile liquid-filled ion-selective electrodes into solid-contactelectrodes (SCEs) with optimal sensitivity, exceptional selectivity, andfast response time. This new generation of SCEs, based on a layereddevice architecture that includes an electrical contact coated with anion-to-electron transducer, and further protected by an ion-selectivemembrane (ISM), seeks to achieve outstanding analytical performance withstable and robust device design capable of long-term analysis withoutdeterioration in performance.

While recent advancements in the development of ISMs and ion-to-electrontransducing materials have led to significant progress in potentiometricdetection, overcoming the existing chemical limitations of availablematerials capable of forming well-defined interfaces between theelectrode and the ISM may enhance broad implementation of SCEs inchemical sensing.

Achieving stable and reliable measurements using SCEs can depend onseveral conditions, such as: i) reversible ion-to-electron signaltransduction; ii) non-polarizable interface with high exchange currentdensity; iii) absence of any side reactions; and (iv) the absence of athin water layer at the ISM/electrode interface. Efforts to fulfil theaforementioned criteria through the implementation of conductivepolymers and porous carbon-based materials as ion-to-electrontransducers have facilitated major advancements in potentiometry,thereby giving rise to stable and robust potentiometric devices to date.

Nonetheless, the existing classes of materials exhibit trade-offs andlimitations in the context of SCEs. While conductive polymers—such aspoly(octylthiophene) (POT), poly(3,4-ethylenedioxythiophene) (PEDOT) andpolypyrrole (PPy)—can provide hydrophobicity (e.g., contact angle ofwater of 50° and 100° measured on glassy carbon electrode surfacesmodified with either PEDOT-polystyrene sulfonate (PSS) orPpy-perfluorooctanesulfonate, respectively) and high redox capacitance(e.g., 10 μF-200 μl), their performance can also be diminished by: i)variations in the crystallinity that can alter charge transport; ii)dopant-dependent changes in glass transition temperature that may affectmechanical stability of the transducer layer; iii) sensitivity to O₂,CO₂, pH and light that can lead to drift; iv) dependence of conductivityupon conformational changes; and v) slowness of redox influencedconformational changes.

Nanostructured carbon-based materials, such as carbon nanotubes (CNTs),graphene, fullerenes, and three-dimensional ordered mesoporous carbons(3DOM) have been recently shown to perform the function ofion-to-electron signal transduction via the formation of the electricaldouble layer at the membrane/electrode interface. The inherenthydrophobicity of these materials, combined with optimal electricalconductivity and high capacitance (e.g., 625 μl for 3DOM and 302 μl forsingle-walled CNTs), reinforce the advantageous use of nanostructuredmaterials as components for the development of SCEs.

However, several limitations to the use of carbon materials in sensingdevices can also limit their implementation, including: i) limitedcontrol over the structure and electronic properties of thenanostructured carbon materials that may influence the electricalconductivity of the material (e.g., CNTs); ii) requirement for expensiveand sophisticated instrumentation for fabrication; iii) harsh syntheticconditions during the manufacturing process, such as high pressure andtemperature; and iv) limited control over the amount and type ofimpurities introduced during the fabrication process. Despite recentimprovements in fabrication methods of SCEs based on carbon materialsand conductive polymers, fundamental research focused on integratingnovel conductive materials that exhibit the required characteristics ofion-to-electron transduction, high capacitance, and substantialhydrophobicity can promote future advancements in potentiometry.

Moreover, while the signal stability of ISEs can be improved with theapplication of conductive layers, the overall performance of ISEs isnonetheless dictated by the ion-selective membrane. This approach allowsa full utilization of existing ion recognition centers and membraneformulations to produce potentiometric sensors with optimal sensitivityand selectivity towards targeted analytes. However, the operationallifetime of these electrodes is highly dependent on the solubility ofthe components in the polymeric matrix and is further limited by theirleaching out of the membrane.

Over several years, large advancements in analytical and organicchemistry offered a vast number of approaches to minimize the extent towhich the active components diffuse out of the sensing layer, andconsequently, to improve the performance of potentiometric sensors. Themost logical and intuitive approach involved chemical modifications ofsensing components such as the addition of long alkyl chains to improvethe hydrophobicity of studied molecules or their direct attachment tothe polymer backbone to minimize or prevent leaching. However, imposedchanges in the solubility of the derivatized molecules often resulted inthe phase separation within the polymeric matrix, while the distributionof covalently attached components within the polymer could not becontrolled using conventional polymerization methods (e.g. free-radicalpolymerization).

Furthermore, the above-described structural modifications are cumbersomeand often involve multistep synthesis. Therefore, structuralmodifications can in turn increase ISE fabrication costs and complexity.

A such, in view of the aforementioned limitations, a need exists for thedevelopment of ion-selective electrodes with a one-component hybridmaterial that simultaneously acts as an ion recognition center and asignal transducer. A need also exists for more facile processes forfabricating the aforementioned ion-selective electrodes. Variousembodiments of the present disclosure address the aforementioned needs.

Similarly, current methods and compositions for capturing ions fromvarious environments suffer from numerous limitations. For instance,existing methods and compositions for capturing ions have limitedadsorption capacity. In particular, the adsorption capacity of existingmaterials for capturing ions (e.g., toxic ions) from variousenvironments (e.g., aqueous environments, such as water) remains verylow.

Existing methods and compositions for capturing ions also have limitedselectivity and adsorption kinetics. For instance, conventionalinorganic sorbents such as layered double hydroxides (LDHs), activatedcarbon, and zeolites are cost effective ion capture materials. However,such materials demonstrate poor selectivity and slow adsorptionkinetics.

Many existing methods and compositions for capturing ions also sufferfrom non-reusability. For instance, organic sorbents such as polymerresins function by reducing and precipitating dichromate ions andthereby get oxidized and decomposed, making these polymer resinsnon-reusable.

Existing methods and compositions for capturing ions also suffer from alack of multi-functionality. For instance, many of the reported ioncapture materials show monofunctional properties, such as either ionsensing or ion capture.

As such, improved methods and compositions are needed for capturing ionsin a more selective, multi-functional, reusable, and efficient manner.Additional embodiments of the present disclosure aim to address theaforementioned need.

In some embodiments, the present disclosure pertains to ion-selectiveelectrodes that include a metal-organic framework and an electrodesurface. The metal-organic framework includes one or more metals and oneor more ligands coordinated with the one or more metals. In addition,the metal-organic framework is associated with the electrode surface ina manner that forms an interface between the metal-organic framework andthe electrode surface. In various embodiments, the ion-selectiveelectrodes of the present disclosure also include a body, apotentiostat, a wiring that electrically connects the electrode surfaceto the potentiostat, and an output display that is electricallyconnected to the potentiostat. In additional embodiments, theion-selective electrodes of the present disclosure also include anion-selective membrane that is associated with a surface of themetal-organic framework.

In more specific embodiments illustrated in FIG. 1A, the ion-selectiveelectrodes of the present disclosure can be in the form of ion-selectiveelectrode 10. In this embodiment, ion-selective electrode 10 includesmetal-organic framework layer 14, electrode surface 12, body 18,potentiostat 22, wiring 20 that electrically connects electrode surface12 to potentiostat 22, and output display 24 that is electricallyconnected to potentiostat 22. Metal-organic framework layer 14 isassociated with electrode surface 12 in such a manner that formsinterface 13 between metal-organic framework layer 14 and electrodesurface 12. In addition, ion-selective electrode 10 can includeion-selective membrane 16 that is associated with a surface ofmetal-organic framework layer 14.

In additional embodiments, the present disclosure pertains to methods ofdetecting an ion in a sample. In some embodiments, the methods of thepresent disclosure utilize the ion-selective electrodes of the presentdisclosure to detect an ion in a sample. In some embodiments illustratedin FIG. 1B, the ion detection methods of the present disclosure includea step of associating the sample with an ion-selective electrode thatincludes a metal-organic framework, an electrode surface, and aninterface between the metal-organic framework and the electrode surface(step 20). Thereafter, the metal-organic framework mediatesion-to-electron transduction through the interface (step 22). Theion-selective electrode detects the presence or absence of the ion inthe sample by detecting a change in potential of the ion-selectiveelectrode (step 24) and correlating the change in the potential to thepresence or absence of the ion (step 26). In some embodiments, themetal-organic framework simultaneously mediates ion sensing andion-to-electron transduction through the interface.

In further embodiments, the present disclosure pertains to methods ofmaking the ion-selective electrodes of the present disclosure. In someembodiments illustrated in FIG. 1C, the methods of the presentdisclosure include a step of associating a metal-organic framework withan electrode surface (step 30) to result in the formation of aninterface between the metal-organic framework and the electrode surface(step 32). In some embodiments, the methods of the present disclosurealso include a step of associating an ion-selective membrane with asurface of the metal-organic framework (step 34).

As set forth in more detail herein, the ion-selective electrodes andmethods of the present disclosure can have numerous embodiments. Inparticular, the ion-selective electrodes of the present disclosure caninclude various types of metal-organic frameworks, electrode surfaces,interfaces, optional ion-selective membranes, and other components.Moreover, various methods may be utilized to detect various ions invarious samples through the use of the ion-selective membranes of thepresent disclosure. In addition, various methods may be utilized tofabricate the ion-selective electrodes of the present disclosure.

Ion-Selective Electrodes

The ion-selective electrodes of the present disclosure generally includea metal-organic framework, an electrode surface, and an interfacebetween the metal-organic frameworks and the electrode surface. In someembodiments, the ion-selective electrodes of the present disclosure alsomay also include an ion-selective membrane. As set forth in more detailherein, the ion-selective electrodes of the present disclosure caninclude various metal-organic frameworks, electrode surfaces,interfaces, and ion-selective membranes. Moreover, the ion-selectiveelectrodes of the present disclosure can include numerous othercomponents.

Metal-Organic Frameworks

The ion-selective electrodes of the present disclosure can includevarious types of metal-organic frameworks. In general, metal-organicframeworks include one or more metals and one or more ligandscoordinated with the one or more metals.

The metal-organic frameworks of the present disclosure can includevarious types of ligands. For instance, in some embodiments, the ligandsinclude, without limitation, organic ligands, hexatopic ligands,polydentate functional groups, aromatic ligands, phthalocyanine-basedligands, metallophthalocyaline-based ligands, naphthalocyanine-basedligands, tridentate ligands, triphenylene-based ligands, triphenylenederivatives, hexahydroxytriphenylene-based organic linkers,hexaiminotriphenlyene-based organic linkers, thiol-based ligands, andcombinations thereof.

In some embodiments, the metal-organic framework ligands includetridentate ligands. In some embodiments, the metal-organic frameworkligands include thiol-based ligands. In more specific embodiments, themetal-organic framework ligands include triphenylene-based ligands. Insome embodiments, the triphenylene-based ligands include, withoutlimitation, 2,3,5,6,10,11-hexahydroxytriphenylene (HHTP),2,3,5,6,10,11-hexaiminotriphenylene (HITP),2,3,5,6,10,11-hexathiotriphenylene (HTTP), and combinations thereof.

The metal-organic framework ligands can have various structures. Forinstance, in some embodiments, the metal-organic framework ligands havesemiquinone structures. In some embodiments, the metal-organic frameworkligands have quinone structures. In some embodiments, the metal-organicframework ligands include ion binding moieties. In some embodiments, theion binding moieties are specific for a particular ion to be detected bythe methods of the present disclosure.

The metal-organic frameworks of the present disclosure can also includevarious types of metals. For instance, in some embodiments, themetal-organic framework metals include, without limitation, divalentmetals, transition metals, iron, nickel, copper, cobalt, zinc,manganese, platinum, palladium, gold, bismuth, chromium, magnesium, tin,and combinations thereof.

The metal-organic framework metals may be in various forms. Forinstance, in some embodiments, more than one type of metal may be usedat once within the same metal-organic framework. In some embodiments,the metal-organic framework metals may be in the form of at least one ofmetal ions, metal clusters, metallic nodes, metal catecholates, metalsalts, and combinations thereof.

In more specific embodiments, the metal-organic framework metals includedivalent metal ions. In some embodiments, the divalent metal ionsinclude, without limitation, cobalt (II), nickel (II), copper (II), andcombinations thereof.

In additional embodiments, the metal-organic framework metals includenickel. In some embodiments, the nickel may be in the form of at leastone of nickel (II) nodes, Ni(OAc)₂, NiCl₂, and combinations thereof.

Various ligands and metals may be combined to form various metal-organicframeworks. For instance, in some embodiments, the metal-organicframeworks of the present disclosure include, without limitation,Co₃HTTP₂, Ni₃HTTP₂, Cu₃HTTP₂, Co₃HHTP₂, Ni₃HHTP₂, Cu₃HHTP₂, andcombinations thereof.

The metal-organic frameworks of the present disclosure can includevarious structures. For instance, in some embodiments, the metal-organicframeworks of the present disclosure have a porous structure. In someembodiments, the metal-organic frameworks of the present disclosureinclude a plurality of micropores that have diameters of less than orabout 2 nm. In some embodiments, the metal-organic frameworks of thepresent disclosure include a plurality of micropores with diameters ofless than about 2 nm. In some embodiments, the metal-organic frameworksof the present disclosure include a plurality of micropores withdiameters of about 2 nm.

In some embodiments, the metal-organic frameworks of the presentdisclosure have a two-dimensional structure. In some embodiments, themetal-organic frameworks of the present disclosure are in the form of apacked network.

In some embodiments, the metal-organic frameworks of the presentdisclosure are in crystalline form. For instance, in some embodiments,the metal-organic frameworks include a long range crystalline order. Insome embodiments, the metal-organic frameworks are in the form ofcrystallites. In some embodiments, the metal-organic frameworks are inthe form of porous and ordered crystalline frameworks. In someembodiments, the metal-organic frameworks are in the form of porouscoordination polymers with limited or no crystallinity.

In some embodiments, the metal-organic frameworks are arranged in theform of a lattice. In some embodiments, the metal-organic frameworks arearranged in the form of a two-dimensional Kagome lattice.

The metal-organic frameworks of the present disclosure may also havevarious shapes. For instance, in some embodiments, the metal-organicframeworks are in the form of nanorods. In some embodiments, themetal-organic frameworks are in the form of rod-shapes crystallites. Insome embodiments, the metal-organic frameworks can be in the form ofsheets or irregular shapes.

In some embodiments, the metal-organic frameworks of the presentdisclosure may be in the form of a layer, a powder, a compressed powder,a pellet, a pencil-lead, a free-standing film, a substrate-supportedfilm, or combinations of such forms. In some embodiments, themetal-organic frameworks of the present disclosure are in the form of alayer, such as a stacked layer structure. In some embodiments, themetal-organic framework layer has a thickness ranging from about 10microns to about 100 microns. In some embodiments, the metal-organicframework layer has a thickness ranging from about 20 microns to about65 microns. In some embodiments, the metal-organic framework layer has athickness of about 20 microns, a thickness of about 40 microns, or athickness of about 65 microns.

The metal-organic frameworks of the present disclosure can also includevarious surface areas. For instance, in some embodiments, themetal-organic frameworks constitute a surface area ranging from about 10m²/g to about 1,000 m²/g. In some embodiments, the metal-organicframeworks have a surface area ranging from about 50 m²/g to about 500m²/g. In some embodiments, the metal-organic frameworks have a surfacearea ranging from about 300 m²/g to about 500 m²/g. In some embodiments,the metal-organic frameworks have a surface area ranging from about 400m²/g to about 500 m²/g.

The metal-organic frameworks of the present disclosure can have variousphysical properties. For instance, in some embodiments, themetal-organic frameworks of the present disclosure have a net neutralcharge. In some embodiments, the metal-organic frameworks of the presentdisclosure have a net neutral charge in the absence of potentiallycharge-balancing counter-ions. In some embodiments, the metal-organicframeworks of the present disclosure have a negative charge in thepresence of charge-balancing cations. In some embodiments, the metalorganic-frameworks of the present disclosure have a positive charge inthe presence of charge-balancing anions.

The metal-organic frameworks of the present disclosure can also havevarious ion selectivities. In some embodiments, the metal-organicframeworks of the present disclosure have different ion selectivitiesbased on different metal-organic framework contents. For instance, insome embodiments, metal-organic frameworks may be selective forparticular cations or anions. In more specific embodiments,metal-organic frameworks that include Cu₃HHTP₂ may be selective forcopper ions. In some embodiments, metal-organic frameworks that includeNi₃HHTP₂ may be selective for NO₃ ⁻ ions.

The metal-organic frameworks of the present disclosure can also havevarious electrical properties. For instance, in some non-limitingembodiments, the metal-organic frameworks of the present disclosure havea capacitance of at least about 200 μF. In some embodiments, themetal-organic frameworks of the present disclosure have a capacitance ofat least about 150 μF. In some embodiments, the metal-organic frameworksof the present disclosure have a capacitance of at least about 100 μF.In some embodiments, the metal-organic frameworks of the presentdisclosure have a capacitance of at least about 20 μF.

The metal-organic frameworks of the present disclosure can serve variousfunctions in the ion-selective electrodes of the present disclosure. Forinstance, in some embodiments, the metal-organic frameworks of thepresent disclosure serve as an ion membrane for capturing ions. In someembodiments, the metal-organic frameworks of the present disclosurecapture ions through chelation. In some embodiments, the metal-organicframeworks of the present disclosure capture ions in ion-selectiveelectrodes that lack any additional ion-selective membranes, conductivelayers or components for capturing ions.

In some embodiments, the metal-organic frameworks of the presentdisclosure can mediate ion-to-electron transduction through interfaceregions between the metal-organic frameworks and electrode surfaces ofion-selective electrodes. In some embodiments, the metal-organicframeworks of the present disclosure mediate ion-to-electrontransduction through the interface regions between metal-organicframeworks and electrode surfaces by transducing a charge in the form ofions through the interface and onto the electrode surface in the form ofelectrons. In some embodiments, the ion-to-electron transduction occursreversibly.

In some embodiments, the metal-organic frameworks of the presentdisclosure can simultaneously serve as an ion recognition sensor and anion-to-electron transducer. For instance, in some embodiments, themetal-organic frameworks of the present disclosure are able tosimultaneously recognize ions in a sample and transduce the ions into anelectronic signal for recordation by the ion-selective electrodes of thepresent disclosure.

In some embodiments, the ability of metal-organic frameworks of thepresent disclosure to simultaneously serve as an ion recognition sensorand an ion-to-electron transducer can significantly improve thepotential stability of the ion-selective electrodes of the presentdisclosure. In some embodiments, the aforementioned ability maycircumvent the need for the ion-selective electrodes of the presentdisclosure to contain a separate ion-selective membrane.

In some embodiments, the metal-organic frameworks of the presentdisclosure serve as an electrode or an electrode component (e.g.,electrode surface). For instance, in some embodiments, conductivemetal-organic frameworks can have a direct function as a porouselectrode. In some embodiments, the metal-organic frameworks of thepresent disclosure can simultaneously serve as an ion recognitionsensor, an ion-to-electron transducer, and an electrode (e.g., aconductive electrode or an electrode component, such as an electrodesurface). In some embodiments, the aforementioned ability may allow forthe ion-selective electrodes of the present disclosure to achievepotentiometric detection in a more facile manner while circumventing theneed for additional ion-selective electrode components.

Electrode Surfaces

The metal-organic frameworks of the present disclosure may be associatedwith electrode surfaces of ion-selective membranes in various manners.For instance, in some embodiments, metal-organic frameworks areassociated with electrode surfaces in such a manner that allowsmetal-organic frameworks to serve as both an ion recognition sensor andan ion-to-electron transducer.

In some embodiments, the metal-organic frameworks are conformally coatedon an electrode surface. In some embodiments, the metal-organicframeworks are integrated onto the electrode surface. In someembodiments, the metal-organic frameworks form a layer on an electrodesurface. In some embodiments, the metal-organic frameworks are in ohmiccontact with an electrode surface.

The electrode surfaces of ion-selective membranes can be in variousforms. For instance, in some embodiments, the electrode surface is inthe form of a conductive substrate. In some embodiments, the conductivesubstrate is in the form of a transparent conductive film. In morespecific embodiments, the electrode surface is in the form of a goldconductive substrate, carbon conductive substrate, copper substrate,platinum substrate, or combinations thereof.

In additional embodiments, the metal-organic frameworks of the presentdisclosure serve as the electrode surface. For instance, in someembodiments, a surface of the metal-organic frameworks of the presentdisclosure serves as the electrode surface. In some embodiments, themetal-organic frameworks of the present disclosure serve as theelectrode surface in the form of a conductive substrate.

Interfaces

In the present disclosure, interfaces generally refer to regions of anion-selective electrode between an electrode surface and metal-organicframeworks (e.g., interface 13 shown in FIG. 1A). In some embodimentswhere metal-organic frameworks serve as the electrode surface, theinterface may represent a region within the metal-organic frameworks.

The interfaces of the present disclosure can have various properties.For instance, in some embodiments, the interface is hydrophobic. In someembodiments, the interface is non-polarizable. In some embodiments, theinterface has low contact resistance. In some embodiments, the interfaceis non-polarizable and has high exchange current density.

In some embodiments, the interfaces of the present disclosure can havevarious advantageous effects. For instance, in some embodiments, theinterfaces of the present disclosure can further facilitateion-to-electron transduction through the interface regions.

Ion-Selective Membrane

In some embodiments, the ion-selective electrodes of the presentdisclosure can also include an ion-selective membrane (e.g.,ion-selective membrane 16 in FIG. 1A). In some embodiments, theion-selective membrane is utilized to capture an ion.

The ion-selective membranes of the present disclosure may be positionedat various regions of the ion-selective electrodes. For instance, insome embodiments, the ion-selective membrane is associated with asurface of metal-organic frameworks. In some embodiments, themetal-organic framework surface that is associated with theion-selective membrane is a surface opposite of the metal-organicframework surface associated with the electrode surface.

The ion-selective membranes of the present disclosure may be associatedwith metal-organic frameworks in various manners. For instance, in someembodiments, the ion-selective membrane is coated on a surface ofmetal-organic frameworks. In some embodiments, the association of anion-selective membrane with metal-organic frameworks forms an additionalinterface region, such as a low contact resistance interface region.

The ion-selective electrodes of the present disclosure may includevarious types of ion-selective membranes. For instance, in someembodiments, the ion-selective membranes of the present disclosureinclude, without limitation, cation-selective membranes, anion-selectivemembranes, and combinations thereof. In some embodiments, theion-selective membrane is a polymer-based membrane. In some embodiments,the polymer-based membrane includes, without limitation,poly(octylthiophene) (POT), poly(3,4-ethylenedioxythiophene) (PEDOT),polypyrrole (PPy), polystyrene sulfonate (PSS), polyvinyl chloride(PVC), poly(methyl) methacrylate (PMMA), poly(decyl) methacrylate (PDMA)and combinations thereof.

In some embodiments, the ion-selective membrane includes one or moremolecules. In some embodiments, the ion-selective membrane includes,without limitation, ionophores (ion-chelator), ion-exchangers,plasticizers, polymers, and combinations thereof. In some embodiments,the molecules include, without limitation, sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB),bis(2-ethylhexyl) sebacate (DOS), tridodecylmethylammonium chloride(TDMACl), and combinations thereof.

In some embodiments, the ion-selective membrane is selective for aparticular ion. In some embodiments, the ion-selective membrane isselective for a cation. In more specific embodiments, the ion-selectivemembrane is a potassium-selective membrane. In some embodiments, thepotassium-selective membrane includes, without limitation, potassiumionophore II, sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate(NaTFPB), high molecular weight polyvinyl chloride (PVC),bis(2-ethylhexyl) sebacate (DOS), and combinations thereof.

In some embodiments, the ion-selective membrane is selective for ananion. In more specific embodiments, the ion-selective membrane is anitrate-selective membrane that includes, without limitation,tridodecylmethylammonium chloride (TDMACl), high molecular weightpolyvinyl chloride (PVC), bis(2-ethylhexyl) sebacate (DOS), andcombinations thereof.

Additional Electrode Components

In various embodiments, the ion-selective electrodes of the presentdisclosure can also include additional electrode components. Forinstance, in some embodiments, the ion-selective electrodes of thepresent disclosure can include a body (e.g., body 18 shown in FIG. 1A).In some embodiments, the body is a polymer-based body, such as a bodycomposed of polyvinyl chloride (PVC). In some embodiments, the body is aTeflon-based body.

In some embodiments, the ion-selective electrodes of the presentdisclosure can also include a potentiostat (e.g., potentiostat 22 shownin FIG. 1A). In some embodiments, the ion-selective electrodes of thepresent disclosure can also include a wiring (e.g., wiring 20 shown inFIG. 1A) that electrically connects the electrode surface to thepotentiostat. In some embodiments, the wiring is a copper wiring. Insome embodiments, the ion-selective electrodes of the present disclosurecan also include an output display (e.g., output display 24 in FIG. 1A)that is electrically connected to the potentiostat.

Ion-Selective Electrode Structures and Properties

The ion-selective electrodes of the present disclosure can includevarious structures and properties. For instance, in some embodiments,the ion-selective electrodes of the present disclosure have a layeredstructure. In some embodiments, the ion-selective electrodes of thepresent disclosure are substantially hydrophobic. In some embodiments,the ion-selective electrodes of the present disclosure are resistive tochanges induced by the presence of various environmental factors, suchas oxygen, N₂, and light.

In some embodiments, the ion-selective electrodes of the presentdisclosure exhibit optimal capacitance. For instance, in someembodiments, the ion-selective electrodes of the present disclosureexhibit capacitance of more than about 200 μF.

In some embodiments, the ion-selective electrodes of the presentdisclosure exhibit optimal potential stability. For instance, in someembodiments, the ion-selective electrodes of the present disclosureexhibit a potential stability drift of about 10-12 μA/h under polarizingcondition of 1 nA.

In some embodiments, the ion-selective electrodes of the presentdisclosure exhibit near-Nernstian behavior. For instance, in someembodiments, the ion-selective electrodes of the present disclosureexhibit near-Nernstian behavior of about 50-60 mV/sec.

The ion-selective electrodes of the present disclosure may be in variousforms. For instance, in some embodiments, the ion-selective electrodesof the present disclosure may include, without limitation, carbonelectrodes, glassy carbon electrodes, gold electrodes, solid contactelectrodes, and combinations thereof. In more specific embodiments, theion-selective electrodes of the present disclosure may include glassycarbon electrodes.

Methods of Detecting Ions in a Sample

In additional embodiments, the present disclosure pertains to methods ofdetecting an ion in a sample. In some embodiments, the methods of thepresent disclosure include a step of associating the sample with anion-selective electrode of the present disclosure such that themetal-organic framework of the ion-selective electrode mediatesion-to-electron transduction through the interface between metal-organicframeworks and the electrode surface. Thereafter, the ion-selectiveelectrode detects the presence or absence of the ion in the sample bydetecting a change in potential of the ion-selective electrode andcorrelating the change to the presence or absence of the ion.

As set forth in more detail herein, various methods may be utilized toassociate various samples containing various ions with variousion-selective electrodes. Moreover, various methods may be utilized todetect the presence or absence of ions in a sample.

Samples

The methods of the present disclosure may be utilized to detect ionsfrom various samples. The samples may be in various forms. For instance,in some embodiments, the sample is in gaseous form, liquid form, solidform, or combinations of such forms. In some embodiments, the sample isin liquid form. In some embodiments, the sample is in the form of anaqueous solution.

In some embodiments, the sample is in solid form. In some embodiments,the sample is in the form of a membrane. In some embodiments, themembrane is associated with a surface of the metal-organic framework.

Detection of Ions

The methods of the present disclosure may be utilized to detect variousions from samples. For instance, in some embodiments, the ion to bedetected includes, without limitation, anions, cations and combinationsthereof.

In some embodiments, the ion to be detected includes a cation. In someembodiments, the cation includes, without limitation, Ca²⁺, Co²⁺, Mg²⁺,Zn²⁺, Pb²⁺, Ni²⁺, Cu²⁺, Na⁺, K⁺, NH₄ ⁺, and combinations thereof.

In some embodiments, the ion to be detected includes an anion. In someembodiments, the anion includes, without limitation, CH₃COO⁻, NO₃ ⁻,ClO₄ ⁻, Cl⁻, I⁻, F⁻, Br⁻, SO₄ ²⁻, S₂O₈ ²⁻, Cr₂O₇ ²⁻, and combinationsthereof.

Association of Samples with Ion-Selective Electrodes

Various methods may be utilized to associate samples with ion-selectiveelectrodes. For instance, in some embodiments, the association occurs byflowing the sample through an ion-selective electrode. In someembodiments, the association occurs by incubating the sample with theion-selective electrode.

In some embodiments, the association of a sample with ion-selectiveelectrodes occurs in an active manner, where an active step is taken toassociate samples with the ion-selective electrodes (e.g., activelyflowing the sample through the ion-selective electrodes). In someembodiments, the association occurs in a passive manner, such as throughthe passive incubation of the ion-selective electrodes with the sample.

The association of a sample with ion-selective electrodes can occur invarious manners. For instance, in some embodiments, the associationresults in the reversible association of any ion in the sample with themetal-organic frameworks of the ion-selective electrodes. In someembodiments, the association results in the selective association of aspecific ion in the sample with the metal-organic frameworks ofion-selective electrodes.

In some embodiments, the association also results in filtration,pre-concentration, and capture of ions in a sample by the metal-organicframeworks of the ion-selective electrodes. In some embodiments, theassociation, filtration, pre-concentration and capture of the ions occursimultaneously.

Detection of a Change in Potential of the Ion-Selective Electrodes

Various methods may also be utilized to detect a change in potential ofthe ion-selective electrodes. For instance, in some embodiments, thechange in the potential of the ion-selective electrode is detected bydetecting a change in voltage of the ion-selective electrode over time.

In some embodiments, the change in the potential of the ion-selectiveelectrode is detected by detecting a change in voltage of theion-selective electrode over time when compared to a reference electrodenot associated with the sample. In some embodiments, the detected changein voltage is represented by an increase in voltage over time. In someembodiments, the detected change in voltage is represented by a decreasein voltage over time.

Additional methods of detecting a change in potential of theion-selective electrodes can also be envisioned.

Correlating a Change in Potential to Presence or Absence of Ions

Various methods may also be utilized to correlate a change in potentialof ion-selective electrodes to the presence or absence of an ion. Forinstance, in some embodiments, the change in the potential of theion-selective electrode is correlated to the presence or absence of anion by comparing the change in the potential to the change in potentialof the ion-selective electrode in response to known ions. In someembodiments, the change in the potential of the ion-selective electrodeis correlated to the presence or absence of an ion by comparing thechange in the potential to potentiometric slopes of known ions.

Additional methods of correlating a change in potential of ion-selectiveelectrodes to the presence or absence of an ion can also be envisioned.

Modes of Ion Detection

The methods of the present disclosure can be utilized to detect ions invarious manners. For instance, in some embodiments, the methods of thepresent disclosure can be utilized to detect a single ion. In someembodiments, the methods of the present disclosure can be utilized todetect multiple ions.

In some embodiments, the methods of the present disclosure can beutilized to detect the concentration of an ion. For instance, in someembodiments, ions may be detected at concentrations of less than about7×10⁻⁷ M. In some embodiments, ions may be detected at concentrations ofless than about 6×10⁻⁷ M.

Without being bound by theory, the methods of the present disclosure canbe utilized to detect ions through various mechanisms. For instance, insome embodiments that were described previously, the metal-organicframeworks of ion-selective electrodes mediate ion-to-electrontransduction through the interface between metal-organic frameworks andthe electrode surface in order to detect ions. In some embodiments thatwere also described previously, the metal-organic frameworks ofion-selective electrodes simultaneously mediate ion sensing andion-to-electron transduction through the interface in order to detections.

Methods of Making Ion-Selective Electrodes

Additional embodiments of the present disclosure pertain to methods ofmaking the ion-selective electrodes of the present disclosure. In someembodiments, the methods of the present disclosure include a step ofassociating a metal-organic framework with an electrode surface toresult in the formation of an interface between the metal-organicframework and the electrode surface.

Various methods may be utilized to associate metal-organic frameworkswith an electrode surface. For instance, in some embodiments, theassociation occurs by applying a dispersion of metal-organic frameworksonto the electrode surface. In some embodiments, the metal-organicframeworks are in a solvent. In some embodiments, the solvent is anorganic solvent, such as acetonitrile.

In some embodiments, the association occurs by drop-casting ametal-organic framework dispersion onto the electrode surface. In someembodiments, the association occurs by compressing a metal-organicframework powder onto the electrode surface. In some embodiments, theassociation occurs by spin-coating a metal-organic framework dispersiononto the electrode surface. In some embodiments, the association occursby electrodeposition of a metal-organic framework from ligand and metalcomponents in solution.

In some embodiments, the methods of the present disclosure also includea step of associating an ion-selective membrane with a surface ofmetal-organic frameworks. In some embodiments, the aforementionedassociation steps may also be utilized to associate an ion-selectivemembrane with a surface of metal-organic frameworks.

The ion-selective electrode fabrication methods of the presentdisclosure may be utilized to control the ion selectivity of the formedelectrodes. For instance, in some embodiments, selectivity of theion-selective electrode to different ions can be controlled by selectingmetal-organic frameworks with metal nodes that are specific for aparticular ion. In some embodiments, selectivity of the ion-selectiveelectrode to different ions can be controlled by selecting metal-organicframeworks with ligands that are selective for a particular ion. Forinstance, in some embodiments, the selected metal-organic frameworks mayhave ligands with ion-binding moieties that are specific for aparticular ion.

In some embodiments, selectivity of the ion-selective electrodes todifferent ions can be controlled by selecting metal-organic frameworkswith particular pore sizes. In some embodiments, selectivity of theion-selective electrodes to different ions can be controlled byselecting metal-organic frameworks with metals that are selective for aparticular ion.

Methods and Compositions for Capturing Ions from an Environment

Additional embodiments of the present disclosure pertain to compositionsfor capturing ions. Such compositions generally include metal-organicframeworks. Further embodiments of the present disclosure pertain tomethods of capturing one or more ions from an environment. In someembodiments illustrated in FIG. 1D, the methods of the presentdisclosure include associating the environment with a composition of thepresent disclosure (step 40) to result in the capture of the one or moreions by the metal-organic frameworks in the composition (step 42). Insome embodiments, the methods of the present disclosure also include astep of detecting the one or more captured ions (step 44). In someembodiments, the methods of the present disclosure also include a stepof reusing the composition for the capture of additional ions (step 46).

As set forth in more detail herein, the ion capture methods andcompositions of the present disclosure can have numerous embodiments.

Metal-Organic Frameworks

The ion capture methods and compositions of the present disclosure canutilize and include various types of metal-organic frameworks. Suitablemetal-organic frameworks were described supra. For instance, in someembodiments, the metal-organic frameworks include one or more metals andone or more ligands coordinated with the one or more metals.

The metal-organic frameworks of the present disclosure can includevarious types of metals. For instance, in some embodiments, the one ormore metals include metals with open metal sites. In some embodiments,the open metal sites represent open coordination sites (i.e.,coordinatively unsatured sites) that are operational to coordinate withions. In some embodiments, the one or more metals include, withoutlimitation, divalent metals, transition metals, iron, nickel, copper,cobalt, zinc, manganese, platinum, palladium, gold, bismuth, chromium,magnesium, tin, and combinations thereof. In some embodiments, the oneor more metals include, without limitation, nickel, copper, andcombinations thereof. In some embodiments, the one or more metalsinclude nickel.

The metal-organic frameworks of the present disclosure can also includevarious types of ligands. For instance, in some embodiments, the one ormore ligands include, without limitation, organic ligands, hexatopicligands, polydentate functional groups, aromatic ligands,phthalocyanine-based ligands, metallophthalocyaline-based ligands,naphthalocyanine-based ligands, tridentate ligands, triphenylene-basedligands, triphenylene derivatives, hexahydroxytriphenylene-based organiclinkers, hexaiminotriphenlyene-based organic linkers, thiol-basedligands, and combinations thereof.

In some embodiments, the one or more ligands include one or morearomatic ligands. In some embodiments, the one or more aromatic ligandsmay be operational for interacting with ions. In some embodiments, theone or more aromatic ligands may interact with ions throughπ-interactions, such anion-π and cation-π interactions. In someembodiments, the one or more aromatic ligands include one or morepolycyclic aromatic ligands. In some embodiments, the one or morepolycyclic aromatic ligands include one or more connected aromaticrings.

In some embodiments, the one or more ligands (e.g., aromatic ligands)include one or more hexatopic ligands. In some embodiments, the one ormore ligands include one or more triphenylene-based ligands. In someembodiments, the one or more triphenylene-based ligands include, withoutlimitation, hexatopic triphenylene-based ligands,2,3,5,6,10,11-hexahydroxytriphenylene (HHTP),2,3,5,6,10,11-hexaiminotriphenylene (HITP),2,3,5,6,10,11-hexathiotriphenylene (HTTP), and combinations thereof. Insome embodiments, the one or more triphenylene-based ligands includehexatopic triphenylene-based ligands. In some embodiments, the one ormore triphenylene-based ligands include, without limitation,2,3,5,6,10,11-hexahydroxytriphenylene (HHTP),2,3,5,6,10,11-hexaiminotriphenylene (HITP), and combinations thereof. Insome embodiments, the one or more ligands include, without limitation,2,5-dioxido-1,4-benzenedicarboxylic acid, tetrahydroxy-1,4-benzoquinone,hexaaminobenzene, and combinations thereof.

In some embodiments, the one or more ligands include functional groupscoupled to the ligands (e.g., aromatic ligands). In some embodiments,the functional groups include functional groups that are operational tointeract with ions. In some embodiments, the functional groups pointtowards metal-organic framework pores. In some embodiments, thefunctional groups may interact with the ions through hydrogen bondsbetween hydrogen atoms of the functional groups and ion atoms (e.g.,oxygen atoms). In some embodiments, the functional groups include,without limitation, hydroxy groups, amine groups, thiol groups,coordinated groups thereof, deprotonated groups therefore, andcombinations thereof.

In some embodiments, the metal-organic frameworks of the presentdisclosure include a plurality of metals and a plurality of ligands. Insome embodiments, the metals are interconnected through the plurality ofthe ligands. In some embodiments, the metal-organic frameworks include aplurality of metals and a plurality of ligands coordinated with theplurality of metals. In some embodiments, the metal-organic frameworksinclude a plurality of metals and a plurality of aromatic ligandscoordinated with the plurality of metals. In some embodiments, themetal-organic frameworks of the present disclosure include a pluralityof metals and a plurality of triphenylene-based ligands. In someembodiments, the metals are interconnected through the plurality of thetriphenylene-based ligands. In some embodiments, the metal-organicframeworks of the present disclosure include, without limitation,Co₃HTTP₂, Ni₃HTTP₂, Cu₃HTTP₂, Co₃HHTP₂, Ni₃HHTP₂, Cu₃HHTP₂, andcombinations thereof. In some embodiments, the metal-organic frameworksof the present disclosure include, without limitation, Ni₃(HHTP)₂,Ni₃(HITP)₂, CU₃(HHTP)₂, Cu₃(HITP)₂, and combinations thereof. In someembodiments, the metal-organic frameworks of the present disclosureinclude Ni₃(HITP)₂. In some embodiments, the metal-organic frameworks ofthe present disclosure include, without limitation, MFU-4L type MOFs,MOF-74, and combinations thereof.

The metal-organic frameworks of the present disclosure may be in variousforms. For instance, in some embodiments, the metal-organic frameworksof the present disclosure are in the form of a membrane. In someembodiments, the metal-organic frameworks of the present disclosureinclude a layered structure. In some embodiments, the layered structureincludes a multi-layered and stacked structure.

In some embodiments, the metal-organic frameworks of the presentdisclosure are in the form of a two-dimensional and conductive network.In some embodiments, the metal-organic framework is in crystalline form.

Ion Capture

The methods and compositions of the present disclosure may be utilizedto capture various types of ions. For instance, in some embodiments, theone or more ions to be captured include, without limitation, anions,cations and combinations thereof.

In some embodiments, the one or more ions include one or more cations.In some embodiments, the one or more cations include, withoutlimitation, Ca²⁺, Co²⁺, Mg²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Cu²⁺, Na⁺, K⁺, NH₄ ⁺,Hg²⁺ and combinations thereof.

In some embodiments, the one or more ions includes one or more anions.In some embodiments, the one or more anions include one or moreoxyanions. In some embodiments, the one or more anions include, withoutlimitation, CH₃COO⁻, MNO₄ ⁻, NO₃ ⁻, ClO₄ ⁻, Cl⁻, I⁻, F⁻, Br⁻, SO₄ ²⁻,S₂O₈ ²⁻, Cr₂O₇ ²⁻, and combinations thereof.

In some embodiments, the one or more ions includes MNO₄ ⁻. In someembodiments, the one or more ions includes Cr₂O₇ ²⁻.

Ion Capture Capacities

The methods and compositions of the present disclosure can capture ionsat various capacities. For instance, in some embodiments, themetal-organic frameworks of the present disclosure include an ioncapture capacity of more than 300 mg of ion per g of metal-organicframework. In some embodiments, the metal-organic frameworks of thepresent disclosure include an ion capture capacity of more than 400 mgof ion per g of metal-organic framework. In some embodiments, themetal-organic frameworks of the present disclosure include an ioncapture capacity of more than 500 mg of ion per g of metal-organicframework. In some embodiments, the metal-organic frameworks of thepresent disclosure include an ion capture capacity of more than 600 mgof ion per g of metal-organic framework. In some embodiments, themetal-organic frameworks of the present disclosure include an ioncapture capacity of more than 700 mg of ion per g of metal-organicframework. In some embodiments, the metal-organic frameworks of thepresent disclosure include an ion capture capacity of more than 800 mgof ion per g of metal-organic framework.

Environments

The methods and compositions of the present disclosure can capture ionsfrom various environments. For instance, in some embodiments, theenvironment is in a gaseous form, a liquid form, a solid form, orcombinations of such forms.

In some embodiments, the environment is in liquid form. In someembodiments, the liquid environment is in aqueous form. In someembodiments, the liquid environment includes a water stream, such as ariver. In some embodiments, the environment is a sample from anenvironment.

In some embodiments, the sample is in solid form. In some embodiments,the sample is a soil sample.

Association of Environment with Compositions

Various methods may be utilized to associate an environment with thecompositions of the present disclosure. For instance, in someembodiments, the association occurs by flowing the environment through acomposition of the present disclosure. In some embodiments, theassociation occurs by incubating the environment with a composition ofthe present disclosure.

In some embodiments, the association of an environment with acomposition of the present disclosure occurs in an active manner, wherean active step is taken to associate the environment with thecomposition (e.g., actively flowing the environment through thecomposition). In some embodiments, the association occurs in a passivemanner, such as through the passive incubation of the composition withthe environment.

In some embodiments, the association of an environment with acomposition of the present disclosure results in the reversibleassociation of any ion in the environment with the metal-organicframeworks of the compositions. In some embodiments, the associationresults in the selective association of a specific ion in theenvironment with the metal-organic frameworks of the compositions. Insome embodiments, the association also results in filtration andpre-concentration of ions from an environment by the compositions of thepresent disclosure.

Reusability and Multi-Functionality

The compositions of the present disclosure can include variousadvantageous properties. For instance, in some embodiments, thecompositions of the present disclosure may be reusable. As such, in someembodiments, the methods of the present disclosure also include a stepof reusing the compositions of the present disclosure for additional ioncapture. In some embodiments, the captured ions may be removed (e.g.,eluted) from the metal-organic frameworks prior to additional ioncapture.

In some embodiments, the compositions of the present disclosure may alsobe operational for detecting one or more of the captured ions. As such,in some embodiments, the methods of the present disclosure also includea step of detecting one or more of the captured ions. In someembodiments, the detecting occurs by detecting a change in potential ofthe metal-organic frameworks in the composition and correlating thechange in the potential to the presence of the one or more ions. In someembodiments, the detection includes detecting of a change in currentpassing through the metal-organic framework and correlating the changein the current to the presence of the one or more ions.

In some embodiments, the metal-organic frameworks in the compositions ofthe present disclosure may be a component of an ion-selective electrode.Suitable ion-selective electrodes were described supra. For instance, insome embodiments, the ion-selective electrode includes the metal-organicframework and an electrode surface. In some embodiments, themetal-organic framework is associated with the electrode surface in amanner that forms an interface between the metal-organic framework andthe electrode surface. In some embodiments, the metal-organic frameworkmediates ion-to-electron transduction through the interface.

Applications and Advantages

As set forth in more detail in Examples 1 and 2, Applicants haveidentified at least four advantageous characteristics of theion-selective electrodes and ion detection methods of the presentdisclosure for broad implementation in potentiometry. First, Applicantshave determined that metal-organic frameworks that are associated withthe ion-selective electrodes of the present disclosure (e.g., M₃HHTP₂MOF) possess optimal electrical conductivity, thereby allowing theirimplementation as electrical components in ion-selective electrodes.Second, metal-organic frameworks can be synthesized in a facile mannerby linking inorganic metal ions with ligands through solution-phaseself-assembly to create crystalline frameworks with permanent porosity.Third, conductive metal-organic frameworks have high double layercapacitance that is a function of their large surface area andaccessible nanopores, thus fulfilling the criteria for obtainingion-selective electrodes with high potential stability. Fourth, largedegree of structural control and compositional modularity, achievedthrough bottom-up approaches to fabricating the ion-selective electrodesof the present disclosure, can allow for the integration of specific anddesired ion binding moieties into metal-organic frameworks. Forinstance, the specific ion binding properties in M₃HHTP₂ MOFs may arisefrom the homogenous distribution of oxygen atoms (hard base) within thepores of the conductive network that stabilizes metal ions (hard acids)according to the hard-soft acid-base theory.

As also set forth in more detail in Examples 1 and 2, the ion-selectiveelectrodes and ion detection methods of the present disclosure provideat least three fundamental advances in the area of functional materialdesign for the development of single-component ion-selective electrodesfor the detection of ions (e.g., ionic analytes) in various samples(e.g., aqueous solutions). First, Applicants have demonstrated thatmetal-organic frameworks associated with the ion-selective electrodes ofthe present disclosure can simultaneously act as ion-recognition centersand ion-to-electron signal transducers, thus minimizing the number ofcomponents required to assemble conventional solid-contact ion-selectiveelectrodes. Second, Applicants have demonstrated that, by changing themetal center within a metal-organic framework's network, the nature andmagnitude of response to ions in a sample (e.g., a solution) can bealtered. As such, in some embodiments, the methods of the presentdisclosure can be utilized for the development of single-componention-selective electrodes in which selectivity to different ions could becontrolled through altering the metal nodes in the metal-organicframework.

Third, Applicants have demonstrated that various metal-organicframeworks (e.g., Cu₃HHTP₂ and Ni₃HHTP₂ MOFs) are resistive to changesinduced by the presence of oxygen and light, thus expanding thepotential application of the ion-selective electrodes of the presentdisclosure for prolonged sample monitoring for various purposes (e.g.,environmental analysis). In these configurations, the disclosed sensorsexhibit optimal performance characteristics including near-Nernstianbehavior, wide response range and good signal stability towards manydifferent cations and anions. Moreover, the resulting potentiometricdevices exhibit good signal stability, limited photosensitivity and highresistivity to interfering gases such as oxygen.

As also set forth in more detail in Examples 1 and 2, the ion-selectiveelectrodes of the present disclosure provide at least five practicaladvantages: i) large bulk capacitance; ii) low contact resistance at theinterface between metal-organic frameworks and electrode surfaces or atthe interface between metal-organic frameworks and ion-selectivemembranes; iii) compatibility with the detection of both cations andanions; iv) high potential stability facilitated by the suppression ofthe formation of a water layer at the interface between metal-organicframeworks and electrode surfaces; v) high structural modularity andease of synthesis of different ion-selective electrode components (e.g.,through aqueous self-assembly); vi) reduction in the number ofcomponents required to assemble conventional solid contact ion-selectiveelectrodes; vii) the nature and magnitude of response to ions in asample (e.g., a solution) can be altered by selecting different metalcenters in a metal-organic framework, thus replacing the need forcomplicated optimization protocols; and viii) high resistivity tochanges induced by the presence of oxygen and light.

As such, the ion-selective electrodes and ion detection methods of thepresent disclosure can find numerous applications, such as applicationswhere high signal stability, with ideally no potential drift, isparticularly important. Such applications can include continuousmonitoring of an ion over an extended time period. Such applications canalso include industrial process monitoring, clinical analysis andenvironmental testing. More specific applications can include routinemonitoring of blood potassium, and detection of NO₃ ⁻ in biological andenvironmental samples.

ADDITIONAL EMBODIMENTS

Reference will now be made to more specific embodiments of the presentdisclosure and experimental results that provide support for suchembodiments. However, Applicants note that the disclosure below is forillustrative purposes only and is not intended to limit the scope of theclaimed subject matter in any way.

Example 1. Conductive Metal-Organic Frameworks as Ion-to-ElectronTransducers in Potentiometric Sensors

This Example describes an unexplored property of conductivemetal-organic frameworks (MOFs) as ion-to-electron transducers in thecontext of potentiometric detection. Several conductive two-dimensional(2D) MOF analogs were drop-cast onto a glassy carbon electrode and thencovered with an ion-selective membrane to form a potentiometric sensor.The resulting devices exhibited optimal sensing properties towardsanions and cations, characterized by a near-Nernstian response and overfour order of magnitude linear range. Impedance and chronopotentiometricmeasurements revealed the presence of large bulk capacitance (204.1±2.2μF) and good potential stability (drift of 11.1±0.5 μA/h).Potentiometric water test and contact angle measurements showed thatthis class of materials exhibited hydrophobicity, and inhibited theformation of water layer at the electrode/membrane interface, resultingin a highly stable sensing response with a potential drift as low as11.1 μA/h.

The MOFs that includes metallic nodes (i.e., Ni, Cu and Co)interconnected with triphenylene-based organic linkers(2,3,6,7,10,11-hexahydroxytriphenylene—HHTP) arranged in a Kagomelattice (FIG. 2 ) were integrated into layered device architectures toproduce functional potentiometric devices.

Applicants believe that conductive MOFs possess at least three uniquecharacteristics for potential utility in potentiometry. First, the classof 2D MOFs used in this Example exhibits good conductivity that rivalsthat of carbon-based materials, making them suitable candidates forelectronically transduced signal in analytical devices. Second, beinghighly porous, conductive MOFs have high surface areas on par with thosereported for nanoporous carbons. This characteristic is important forobtaining high capacitance necessary for facilitating ion-to-electrontransduction and obtaining high potential stability. Third, thesematerials can be synthesized from metal ions interconnected with ligandsthrough solution-phase self-assembly to produce highly ordered,crystalline structures. This bottom-up synthetic approach providesstructural control and compositional modularity, facilitating for thedevelopment of conductive materials with predictable and tuneableproperties.

The synthetic control over structure offers a potential advantage overpyrolytic carbons and conductive polymers in terms of chemical controlof batch-to-batch structural reproducibility and application-specifictunability. The synthetic conditions for MOF preparation aresignificantly milder than those typically employed in the synthesis ofporous carbons, and may offer molecular level control of interfaces,materials composition, and device performance. Based on these uniquecharacteristics, Applicants reasoned that conductive MOFs can bedesigned to exhibit ion-to-electron transduction, high capacitance, andsubstantial hydrophobicity desirable for advancing the field ofpotentiometric detection.

Example 1.1. Materials and Instruments

Bis[(benzo-15-crown-5)-15-ylmethyl] pimelate (potassium ionophore II),valinomycin (potassium ionophore I), sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB),tridodecylmethylammonium chloride (TDMACl), high molecular weightpolyvinyl chloride (PVC), bis(2-ethylhexyl) sebacate (DOS) werepurchased from Sigma Aldrich. 2,3,6,7,10,11-hexahydroxytriphenylene(HHTP) was purchased for TCI Chemicals. All chemicals were of analyticalreagent grade. Solutions of metal ions were prepared in ultra-pure waterobtained with Pico Pure 3 water system (resistance 18 MΩ cm⁻¹).

Working solutions of different metal ions were prepared by serialdilutions of a 1 M stock solution. Glassy carbon electrode (3 mm indiameter) were purchased from CH instruments, USA. Scanning ElectronMicroscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) wasperformed using a Hitachi TM3000 SEM (Tokyo, Japan) equipped for X-raymicroanalysis with a Bruker Edax light element Si(Li) detector(Billerica, Mass.). EmStat MUX16 potentiostat (Palm Instruments BV,Netherlands) was used for electrochemistry. The z-dimension (height) forall electrodes were collected using a Zygo NewView 7300 LightInterferometer equipped with a 10× lens. X-ray photoelectronspectroscopy (XPS) experiments were conducted using a PhysicalElectronics Versaprobe II X-ray Photoelectron Spectrometer underultrahigh vacuum (base pressure 10-10 mbar). The measurement chamber wasequipped with a monochromatic A1 (Kα) X-ray source. Both survey andhigh-resolution spectra were obtained using a beam diameter of 200 μm.The spectra were processed with CasaXPS software. Powder X-raydiffraction (PXRD) measurements were performed with a Bruker D8diffractometer equipped with a Ge-monochromated 2.2 kW (40 kV, 40 kA)CuKα (α=1.54 Å) radiation source and a NaI scintillation counterdetector (Billerica, Mass.).

Example 1.2. Synthesis and Characterization of Conductive MOFs

The synthesis of metal-organic frameworks using organic linker2,3,6,7,10,11-hexahydroxytriphenylene was adapted from Yaghi andcoworkers (Chem. Mater. 2012, 24, 3511-3513).

Synthesis of Ni₃HHTP₂. To a 100 mL round bottom flask, 500 mg of HHTPand 767 mg of Ni(OAc)₂.4H₂O were added. 70 mL of deionized water wasthen added to the round bottom flask. The resulting suspension wassonicated for 15 minutes. The reaction mixture was then heated for 24 hat 85° C. under stirring and air. The flask was left to cool for 1 h atroom temperature and the reaction product was filtered with a ceramicfunnel and a filter paper. The solid precipitate was then washed withultra-pure water (1000 mL) and acetone (300 mL). The resulting blackpowder was transferred into a glass vial and dried overnight undervacuum (20 mTorr) at 85° C.

Synthesis of Cu₃HHTP₂. To a 50 mL round bottom flask, 100 mg of HHTP and154 mg of copper (II) trifluoroacetylacetonate were added. 20 mL ofdeionized water was then added to the round bottom flask. The resultingsuspension was sonicated for 15 minutes. The reaction mixture was thenheated for 24 h at 70° C. under stirring and air. The flask was left tocool for 1 h at room temperature and the reaction product was filteredwith a ceramic funnel and a filter paper. The solid precipitate was thenwashed with ultra-pure water (1000 mL) and acetone (300 mL). Theresulting black powder was transferred into a glass vial and driedovernight under vacuum (20 mTorr) at 85° C.

Synthesis of Co₃HHTP₂. To a 50 mL round bottom flask, 50 mg of HHTP and74 mg of CoCl₂.6H₂O were added. 20 mL of deionized water was then addedto the round bottom flask. The resulting suspension was sonicated for 15minutes. The reaction mixture was then heated for 24 h at 70° C. understirring and air. The flask was left to cool for 1 h at room temperatureand the reaction product was filtered with a ceramic funnel and a filterpaper. The solid precipitate was then washed with ultra-pure water (1000mL) and acetone (300 mL). The resulting black powder was transferredinto a glass vial and dried overnight under vacuum (20 mTorr) at 85° C.

Example 1.3. Characterization of M₃HHTP₂ MOFs (M=Co, Ni, Cu)

Scanning electron microscopy (SEM) revealed the presence of distinctrod-shaped crystallites in Ni₃HHTP₂ and Cu₃HHTP₂ MOFs and non-uniformnanoscale morphology in Co₃HHTP₂ MOF (FIGS. 3A-3C). The presence ofmetals (Co, Ni, and Cu) and C, H, O atoms in the bulk of each MOF wasconfirmed by EDX spectroscopy (FIGS. 3A-3C). pXRD revealed stackedlayered structure consistent with previous reports (FIG. 4 ). XPS showedexclusive presence of Ni²⁺ in Ni₃HHTP₂ and mixed valency in Co₃HHTP₂(Co²⁺/Co³⁺) and Cu₃HHTP₂ (Cu¹⁺/Cu²⁺) MOFs with no additionalcounterions, suggesting that the redox-active triphenylene ligandmaintains charge neutrality in the framework (FIGS. 5A-5C, 6A-6C, and7A-7C). These results are consistent with other reports of similarmaterials.

Example 1.4. Preparation of MOF Dispersion

The MOF-dispersion was prepared by transferring 1.0 mg of a selected MOFinto an eppendorf tube containing 1.0 mL of acetonitrile. The same tubewas then sonicated for 4 h at 25° C. to give a homogenous dispersion.

Example 1.5. Preparation of K⁺ and NO₃ ⁻ Sensing Membranes

Traditional potassium selective membranes contained 10 mmol kg⁻¹ ofvalinomycin (K⁺-ISM-I) or potassium ionophore II (K⁺-ISM-II), 5 mmolkg⁻¹ of NaTFPB, 33.3 wt % PVC and 66.6 wt % DOS. NO₃ ⁻-ISM contained 5.0mmol kg⁻¹ of TDMACl, PVC (33.2 wt %) and DOS (66.4 wt %). Theabove-mentioned components were then dissolved in 1.5 mL of THF and theresulting mixture was vortexed for 30 min for complete dissolution.

Example 1.6. Preparation of MOF-Coated Electrodes (GCE/MOF)

The intermediate conductive layer consisting of M₃HHTP₂ MOFs wasprepared by drop casting 5.0 μL aliquots of each conductive MOF directlyonto a solid contact. The electrodes were then dried under nitrogen for3 h before electrochemical measurements were carried out.

Example 1.7. Preparation of ISEs (GCE/MOF/ISM)

For potentiometric measurements, a dispersion of selected MOF (preparedas described in Example 1.4) was drop cast onto the carbon-basedelectrode and dried for 3 h at room temperature. An aliquot (10 μL) ofthe ion-selective membrane was drop cast onto the previously depositedMOF, and the electrodes were left at room temperature to dry overnight.The following day, the resulting ISEs were conditioned in 1.0×10⁻³ Mpotassium chloride solution for 24 h prior to the potentiometric andimpedance experiments. Membrane thicknesses were measured using digitalmicrometer. For the long-term stability test, each electrode was onlyused once (during initial measurement) and then stored in dark, at roomtemperature under air atmosphere, for three weeks in the distilled waterand reused.

Example 1.8. Preparation of Coated Wire Electrodes (GCE/ISM)

Coated wire electrodes (CWEs) were prepared by drop casting (10 μL) ofthe ion-selective membrane suspension directly onto the top of a glassycarbon electrode. Each device was then dried at room temperature for 24h and then immersed in 5 mL of the 1.0×10⁻³ M KCl solution for anadditional 24 h.

Example 1.9. Potentiometric Measurements

Potentiometric responses of all electrodes were recorded using EmStatMUX16 potentiostat (Palm Instruments BV, Netherlands) in a stirredsolution against a double-junction Ag/AgCl reference electrode with a 1M KCl bridge electrolyte (Sigma Aldrich) at room temperature. For allpotentiometric measurements at least three independent NO₃ ⁻ and K⁺-ISEswere used.

Example 1.10. Electrochemical Impedance Spectroscopy

All impedance measurements were performed by using an Ivium TechnologiesCompactStat Impedance Analyser (Ivium Technologies). The EISmeasurements of the deposited MOF layer and ion-selective membranes wereconducted using established techniques. Briefly, impedance spectra werecollected using excitation amplitude of 0.01 V within the frequencyrange spanning from 100 kHz to 0.01 Hz for the GCE/MOF electrodes.However, higher amplitude (0.1 V) was used for electrodes consisting ofa selected MOF-layer and an ion-selective membrane to improve theoverall signal to noise ratio. A conventional three electrodes set-upwas used for all impedance measurements using glassy carbon workingelectrode, platinum auxiliary electrode and a silver-silver chlorideelectrode as the reference. Each measurement was performed atopen-circuit potential in 0.1 M aqueous solution of potassium chlorideat room temperature. All impedance spectra were fitted to equivalentcircuits using the IviumStat software version 2.0. All measurements weredone at least in triplicate.

Example 1.11. Cyclic Voltammetry

Cyclic voltammetry experiments were carried out at room temperature in aconventional three-electrode set-up using Ag/AgCl (1 M) referenceelectrode, platinum wire and glassy carbon as the auxiliary and workingelectrode respectively. 0.1 M KCl was used as background electrolyte forall voltammetric measurements were run under nitrogen atmosphere.

Example 1.12. Chronopotentiometric Characterization

A constant current of −1.0 nA was applied to the working electrode for60 s followed by a reversed current of the same magnitude for the samelength of time. The resulting electromotive force was recorded in asolution of 0.1 M KCl at room temperature. All measurements were carriedout in a three-electrode configuration using the ISEs under Example asworking electrodes. The reference electrode was an Ag/AgCl/KCl (3 M) andthe auxiliary electrode was a platinum wire.

Example 1.13. Measuring the Charge Transfer Resistance, Capacitance, andDiffusional Impedance of Conductive MOFs Using Electrochemical ImpedanceSpectroscopy

To evaluate ion-to-electron transduction, Applicants drop-casted aqueoussuspensions of M₃HHTP₂ MOFs on top of glassy carbon electrodes (GCE) toobtain a layered device. In this configuration, electrochemicalimpedance spectroscopy (EIS) was used to achieve simultaneousmeasurement of three desirable parameters: i) bulk capacitance, ii)charge transfer resistance, and iii) diffusion-induced impedance. FIG.8A illustrates the Nyquist plot of the EIS spectrum recorded in 0.1 MKCl solution for three distinct devices (GCE/MOF) that includes GCEelectrodes with a drop cast layer of Co₃HHTP₂ (blue), Ni₃HHTP₂ (green),and Cu₃HHTP₂ (red) MOFs. This spectrum (FIG. 8A) exhibits three discretefeatures: i) a straight line angled at almost 90° exhibiting only slightcurvature at lower frequencies characteristic of optimal capacitance;ii) the presence of a partial semicircle in the high-to-intermediatefrequency range characteristic of ohmic charge transfer resistance; andiii) lack of Warburg impedance as evidenced by the absence of a lineinclined at 45° in the low frequency range.

The straight line angled at almost 90° in the low frequency region (1Hz-10 mHz; Z′: 280.0Ω to 1.2 kΩ) of the Nyquist plot (FIG. 8A)represents the capacitance of the MOF film. The solution resistance (R1)for 0.1 M KCl was estimated at R1=140Ω, and was consistent with theliterature. The capacitance of the MOF can be computed from the totalimpedance of the electrode at low frequency data (1 Hz-10 mHz) in FIG.8A. Fitting this data with the constant phase element in an equivalentcircuit shown in FIG. 8A gave a substantial capacitance of 204.1±2.2 μF;and phase value of 0.93 for Ni₃HHTP₂ MOF (60±5 μm thickness), 176.6±3.1μF and phase value of 0.84 for the Cu₃HHTP₂ MOF (60±5 μm thickness,FIGS. 9A-9C), and 157.1±1.7 μF and phase value of 0.75 for Co₃HHTP₂ MOF(60±5 μm thickness, FIGS. 9A-9C).

Since, the CPE phase values indicated the behavior of optimal capacitors(phase value of 1), the units of capacitance (Farads) were used instead.Without being bound by theory, Applicants attribute the large values ofrecorded bulk capacitance for all studied MOFs to the presence ofinterconnected nanopores within the MOF lattice that are permeable tothe electrolyte, and the presence of a large number of conductivepathways for electron transport within the drop-cast MOF film. Theserecorded values are within the same order of magnitude as those forconductive polymers, such as PEDOT-PSS (204 μF), or single-walled CNTs(302 μF), and are approximately 10 times lower than one reported forcolloidally imprinted mesoporous (CIM) carbon, which was used tofabricate the most stable ion-selective-electrode to this date. Thelarge magnitude of capacitance of CIM carbon could be attributed to thepresence of large interconnected mesopores (diameter of ˜24 nm) that arereadily accessible for the electrolyte diffusion, in comparison to themicropores found in 2D M₃HXTP₂ MOFs (M=Cu, Ni and Co; diameter of ˜1.8nM), which define the available surface area, and consequentlycapacitance of the MOF.

To examine the dependence of the low frequency capacitance on MOF filmthickness, Applicants prepared three electrodes with differentthicknesses of the conductive Ni₃HHTP₂ MOF layer (20±8 μm, 40±5 μm and60±5 μm) and performed impedance measurements. Increasing the thickness,and consequently the surface area, of the underlying MOF layerintensified the magnitude of capacitance 152.6±1.0 μF, 154.6±0.7 μF, and204.1±2.2 μF for thicknesses of 20±8 μm, 40±5 μm and 60±5 μm,respectively), indicating that this parameter represents a bulkcapacitance of the studied Ni₃HHTP₂ MOFs (FIG. 8B).

The small increase in capacitance of 2.0 μF when the Ni₃HHTP₂ MOF layerthickness was varied from 20±8 μm to 40±5 μm may be a function ofinhomogeneity of the MOF film deposited on the electrode surface. Forexample, the drop-casting method can result in the formation of‘islands’ of material, which may lead to poor electrical contact betweenthe MOF and electrode, thus diminishing the magnitude of observedcapacitance. The increase in capacitance of 49.5 μF with the MOF layerthickness from 40±5 μm to 60±5 μm may arise from the: i) increasedamount of MOF material being available for electrolyte wetting; ii)enhanced electrical contact between the layers of drop-cast MOF and theelectrode; and iii) increase in the density of states in the MOFmaterial.

The presence of small impedance in the high-to-intermediate frequencyregion (100 kHz to 3 Hz; Z′: 44.0Ω-250.0Ω) characterized by the partialsemicircle in FIG. 8B indicated ohmic resistance rather thandouble-layer capacitance as typically observed for ISEs based onconductive polymers. In this electrode configuration, the magnitude ofthis resistance varied with the thickness of deposited conductive MOFlayer (FIG. 8B inset): increasing the thickness of the MOF layer from20±8 μm, 40±5 μm, to 60±5 μm diminished the magnitude of recordedimpedance from 186 Ω, 95Ω to 35Ω, respectively (FIGS. 8B and 10A-10C).

These findings indicate that conductivity of a MOF is the majorcontribution to the ohmic resistance since MOF itself can act aselectronic conductor. Increasing the thickness of the conductive filmwould lead to the increase in the number of possible conductive pathwaysin a layered device, and thus diminish the magnitude of the observedohmic resistance. These observations are consistent with prior findings,demonstrating that the increase in the thickness of the layer of carbonnanotubes correlates with diminished charge transfer resistance inpotentiometric measurements.

Applicants did not observe the characteristic straight line inclined at45° indicative of Warburg impedance associated with thediffusion-limited transport of electrolyte through the pores of thematerial. This observation indicates that ions can diffuse into/throughthe MOF network without the significant contribution from the masstransport resistance.

Additional analysis using cyclic voltammetry (FIGS. 11A-11C andassociated discussion) revealed that the electrochemical behavior ofM₃HHTP₂ MOFs was influenced by the identity of the metal centersembedded within the MOFs, as evidenced by the characteristicallydifferent CV profiles for Ni₃HHTP₂, Cu₃HHTP₂ and Co₃HHTP₂ MOFs (FIGS.11A-11C). The observed voltammetric behavior may be explained by theredox activity of HHTP ligand that can undergo reversible redoxtransformations between catechol, semiquinone, and quinone forms. Giventhat MOFs exhibit permanent porosity, changes in the cumulative porevolume as a function of the MOF layer thickness may be furthermanifested by the unique voltammetry of these materials.

Without being bound by theory, Applicants hypothesize that theelectrochemical double layer charging, characterized by the rectangularshape of the potential-current response, plays a role in the capacitivebehavior of Ni₃HHTP₂ MOF and Co₃HHTP₂-based ISEs. Moreover, the presenceof reversible redox peaks in the cyclic voltammograms of Cu₃HHTP₂/GCEelectrodes, together with large capacitive behavior, as confirmed withEIS measurements, may indicate that the redox pseudo-capacitance is thedominant charge-storage mechanism in Cu₃HHTP₂ MOFs. The presence ofsmall redox peaks in the CV of Ni₃HHTP₂ MOFs may also indicate partialcontribution of redox pseudo-capacitance to the total capacitance inNi₃HHTP₂ MOF, thus providing highest capacitance amongst all studiedM₃HHTP₂ MOF.

To examine whether the presence of the faradaic process influences theimpedance response of the MOFs, Applicants performed EIS measurements atthree different potentials (−0.3 V, 0.0 V, and 0.3 V) for Ni₃HHTP₂. Thechange in magnitude of the applied potential did not significantlyinfluence the outcome of the impedance measurements, indicating therecorded capacitance to be independent of the redox processes observedin cyclic voltammetry (FIG. 12 ). Taken together, these results confirmthat conductive MOF-based materials possess substantial capacitance,ohmic resistance, and charge transfer characteristics suitable forserving the function of ion-to-electron transducers in ISEs, and satisfythe first major criteria in SCE development.

Example 1.14. Quantifying the Efficiency of Ion-to-Electron Transductionby Integrating Conductive MOFs into Solid-State Ion-Selective ElectrodeDevices

Applicants focused subsequent experimental efforts on the use ofNi₃HHTP₂ for the development of stable ISEs due to its highest bulkcapacitance that would facilitate ion-to-electron transduction andprovide substantial signal stability during potentiometric measurements.To assess the function of conductive MOFs as ion-to-electron signaltransducers in potentiometry, Applicants used impedance measurements tocompare the electrochemical performance of two device configurationsfabricated by sequential drop casting of distinct layers (FIG. 13 ). Thefirst device configuration involved the direct deposition of theK⁺-ISM-II on top of glassy carbon electrode (GCE) to create a two-layerdevice: GCE/K⁺-ISM-II (FIG. 13A). The second device configurationemployed a Ni₃HHTP₂ MOF thin film sandwiched between the GCE andK⁺-ISM-II to create a three-layer device (GCE/MOF/K⁺-ISM-II, FIG. 13B)capable of enhanced signal transduction.

For the control GCE/K⁺-ISM-II configuration (FIG. 13A), impedancemeasurements revealed the presence of a small semicircle at highfrequency range followed by the partial arc at lower frequencies (1Hz-10 mHz; Z′: 1.1 MΩ to 12.3 MΩ). Applicants attributed the presence ofthe high-frequency semicircle (100 kHz-1 Hz; Z′: 60.0Ω to 1.0 MΩ) to thebulk resistance in parallel with geometric capacitance of thedrop-casted K⁺-ISM-II. The bulk membrane resistance (1.0±0.2 MΩ) wasextracted from the impedance model shown in FIG. 13A. The second‘larger’ partial semicircle originated from the large charge transferresistance at the interface between the ion-selective membrane andglassy carbon electrode. This second spectral feature indicatedineffective of ion-to-electron transduction in the simple two-layerGCE/K⁺-ISM-II device configuration.

In contrast to FIG. 13A, the impedance spectrum recorded for theGCE/MOF/K⁺-ISM-II devices (FIG. 13B) showed only one high-frequencyspectral component (100 kHz-1 Hz; Z′: 59.0Ω to 1.1 MΩ), which Applicantsattributed to the bulk properties (resistance in parallel with geometriccapacitance) of the ion-selective membrane (1.0±0.3 MΩ). Notably, theabsence of a second semicircle in the low frequency region of thespectrum for the GCE/MOF/K⁺-ISM-II devices was characteristic of the lowcharge transfer resistance at ISM/MOF interface. In addition, cyclicvoltammetry of both device architectures could not be studied due to thehigh resistance of the PVC-based ion-selective membrane. The starkcontrast between FIGS. 13A and 13B suggests that the ion-to-electronsignal transduction at all interfaces, as well as the phase-transfer ofions through the solution/membrane interface in GCE/MOF/K⁺-ISM-II deviceconfiguration, proceeded in a reversible manner and were kineticallyfast. Thus, EIS measurements confirmed that the presence of theconductive MOF between the solid contact and the ion-selective membranestrongly facilitates ion-to-electron signal transduction.

Example 1.15. Potential Stability of MOF-Containing PotentiometricSensors Under Polarizing Conditions

Applicants employed constant current chronopotentiometry to evaluate theability of a representative 2D MOF to provide a non-polarizableinterface with high exchange current density, and thus to improve signalstability of potentiometric devices. High signal stability, with ideallyno potential drift, is particularly important in applications where thecontinuous monitoring of an analyte over an extended time period isrequired. Larger potential drifts (˜1 mV/h) can be tolerated during theshort-term measurements if the electrodes undergo frequent calibrations.To make this assessment, Applicants compared the potential stabilityunder polarizing conditions of two layered device configurationspreviously examined by EIS: a control GCE/K⁺-ISM-II andGCE/MOF/K⁺-ISM-II. Each device was firstly subjected to +1 nA for 60sec, after which the direction of the current was reversed for the sametime interval (−1 nA, 60 sec), and the potential response was recorded.The potential versus time curves (E/t) for the analysed GCE/K⁺-ISM-IIand GCE/MOF/K⁺-ISM-II devices are shown in FIG. 14 . The potential jumpthat occurs during the reversal of applied current can be used directlyto estimate the total resistance of the electrode (Eq. 1)

R=E/I  (Eq. 1)

In this equation, R represents the resistance of the electrode, E ispotential of the electrode and I is the current. The bulk membraneresistance calculated from chronopotentiometric experiments was in closeagreement with data extracted from EIS measurements (1.0 MΩ forGCE/MOF/K⁺-ISM-II electrodes).

The polarizability of the electrodes was further evaluated from theslope (potential over time) at longer times (FIG. 14 ). In the absenceof MOF layer (GCE/ISM), a substantial drift of 2615.0±13.9 μV/sec, underpolarizing conditions (−1 nA applied), was observed. While, the layer ofconductive MOF in the GCE/MOF/K⁺-ISM-II configuration significantlystabilized the electrode resulting in the drift of 14.6±1.1 μV/sec. Thepotential drift (14.6±1.1 μV/sec) estimated from constant-currentchronopotentiometry under polarizing conditions may also be related tothe low frequency capacitance of a solid-contact. Using the E/t curvesto calculate the capacitance of the electrode (E/t=i/C) gave asubstantial capacitance for GCE/MOF/K⁺-ISM-II devices (60.6±1.4 μF),that was 150 times larger than that of GCE/K⁺-ISM-II (0.4±0.1 μF). Theseresults indicate that the MOF conductive layer contributes significantlytowards the potential stability of tested devices under polarizingconditions, and that the stability of fabricated electrodes is on parwith other ISEs based on graphene (14.6 μV drift with 1 nA applied) orsingle-walled CNTs (17.0 μV drift with 1 nA applied).

Example 1.16. Potentiometric Ion Sensing Using Conductive MOFs asIon-to-Electron Transducers

To demonstrate the applicability of conductive MOFs as theion-to-electron transducers in the development of solid-stateion-selective electrodes in this proof-of-concept Example, Applicantsfabricated and evaluated the performance of potassium (model cation) andnitrate (model anion) potentiometric sensors. Routine monitoring ofblood potassium is one of the examples where potassium selectiveelectrodes can make the most significant impact, while the detection ofNO₃ ⁻ has biological and environmental significance.

Applicants employed the electrode configuration in which the MOF layeris drop-casted on the glassy carbon electrode and then covered with anion-selective membrane to produce a potentiometric sensor. Thepotentiometric responses of fabricated NO₃ ⁻-ISM electrodes thatincludes of Ni₃HHTP₂ MOF sandwiched between GCE and NO₃ ⁻-ISM(GCE/MOF/NO₃ ⁻-ISM) are depicted in FIGS. 15A-15B. Near-Nernstianresponses (56.3±0.5 mV decade⁻¹) were observed for all tested electrodeswith the detection limits (6.31±0.01×10⁻⁷ M) and selectivity coefficientvalues closely matching those reported for other solid-contactelectrodes equipped with ISM for nitrate detection (FIGS. 15A-15B and 16and Table 1).

TABLE 1 Selectivity coefficients and experimental slopes obtained forK⁺-ISM-II containg Ni₃HHTP₂ MOF as underlying conductive layer. (K⁺slope = 55.4 ± 0.8 mV). Cation Ca²⁺ Na⁺ NH₄ ⁺ log K^(POT) −3.28 ± 0.02−0.86 ± 0.10 −0.82 ± 0.05 Slope 24.3 ± 1.9 55.7 ± 1.7 54.4 ± 2.1 [mV]

Moreover, tested electrodes demonstrated good short-term (11.1±0.5 μA/h)and long-term potential stability (15 mV change in recorded standardpotential, E°, after 25 days) and exhibited minimal (<1 mV)photosensitivity (FIGS. 17-19 ). In particular, the potential driftestimated from continuous potentiometric measurements for 8 h was11.1±0.5 μA/h, thus confirming optimal potential stability of resultingGCE/MOF/ISM electrodes, whose magnitude is comparable to ISEs based on3DOM carbon (11.7 μA/h) or graphene (12.6 μA/h).

In addition, Applicants observed that the crystallinity of M₃HHTP₂ MOFs(M=Cu, Ni and Co) was retained after potentiometric analysis with MOFsused as ion-to-electron transducers (FIG. 20 ). Applicants' findingsfrom potentiometric and impedance measurements demonstrate thatconductive MOFs can be successfully used as signal transducers for thedevelopment of potentiometric sensors for the detection of cations andanions with promising performance characteristics.

To demonstrate the general applicability of conductive MOFs asion-to-electron transducers in potentiometric detection, Applicantsfabricated K⁺-ISM-II electrodes containing Ni₃HHTP₂ MOF sandwichedbetween GCE and K⁺-ISM-II (GCE/MOF/K⁺-ISM-II). The calibration curve forpotassium ions (FIG. 15B, green triangles) displayed a near-Nernstianslope of 54.1±1.0 mV decade⁻¹ and a micromolar limit of detection of6.76±0.03×10⁻⁶ M. Similar linear response range was obtained for thethree MOF analogues included in this Example, demonstrating the generalapplicability of conductive MOFs in the development of ISEs (FIGS.21A-21C).

Performance characteristics of GCE/MOF/K⁺-ISM-II devices were similar toother potentiometric devices employing analogous K⁺-ISM-II ion-selectivemembranes. Small differences between the reported detection limits ofdevices with similar ISM and those reported here may arise from thepresence of transmembrane ion-fluxes (from the inner filling solution tothe sample) that are readily observed in ISEs based on the liquidcontact.

To confirm that the response characteristics (slope, detection limits)of potassium sensors were primarily a function of the ion-selectivemembrane, rather than the choice of the ion-to-electron transducer,Applicants performed additional sensing experiments by using valinomycinas an ionophore within the ion-selective membrane to generate K⁺-ISEs-I(FIGS. 15A-15B). Applicants observed a near-Nernstian slope of 58.2±1.0mV decade⁻¹ and a nanomolar limit of detection of 5.01±0.01×10⁻⁷ M,which showed an improvement in detection limit compared topotentiometric devices employing this ionophore in conjunction withusing single-walled CNTs (5.00×10⁻⁶ M), graphene (6.31×10⁻⁷ M) or CIMcarbon (3.98×10⁻⁶ M) as ion-to-electron transducers.

The selectivity of potentiometric K⁺ sensors (GCE/MOF/K⁺-ISM-II andGCE/MOF/K⁺-ISM-I) was characterized using an unbiased separate solutionmethod. Each device was firstly conditioned in a solution of lessdiscriminated interfering ions prior to the performed potentiometricmeasurements. Table 2 and FIG. 22 show the selectivity values andcorresponding experimental slopes obtained for Na⁺, NH₄ ⁺ and Ca²⁺ (logK_(POT)-Ca²⁺: −3.28±0.02, Na⁺: −0.86±0.10, and NH₄ ⁺:−0.82±0.05).

TABLE 2 Selectivity coefficients and experimental slopes obtained forNO₃ ⁻-ISM electrodes containg Ni₃HHTP₂ MOF as underlying conductivelayer (NO₃ ⁻ slope = −56.3 ± 0.5 mV). Cation SO₄ ²⁻ Cl⁻ Br⁻ log K^(POT)−3.15 ± 0.01 −1.82 ± 0.01 −0.48 ± 0.05 Slope −28.7 ± 0.9  −55.2 ± 1.3 −55.0 ± 1.0  [mV]

Additional potentiometric analysis of GCE/M₀F/K⁺-ISM-I electrodesrevealed good match with theoretically expected selectivity levels (logK_(POT)-Ca²⁺: −5.46±0.09, Na⁺: −4.10±0.01, and NH₄ ⁺:−2.12±0.05; Table 3and FIG. 23 ). Together, these findings indicate that 2D conductive MOFscan be used to construct sensitive and selective potentiometric sensorswith improved signal stability.

TABLE 3 Selectivity coefficients and experimental slopes obtained forK⁺-ISM-I containg Ni₃HHTP₂ MOF as underlying conductive layer. (K⁺ slope= 57.3 ± 0.2 mV). Cation Ca²⁺ Na⁺ NH₄ ⁺ log K^(POT) −5.46 ± 0.09 −4.10 ±0.01 −2.12 ± 0.05 Slope 25.1 ± 0.9 51.0 ± 0.5 55.9 ± 1.0 [mV]

Example 1.17. Assessing the Potential Stability of GCE/MOF/K⁺-ISM-II andDevices GCE/MOF/NO₃ ⁻-ISM Using the Aqueous Layer Test

A formation of the undesirable water layer at the membrane/electrodeinterface can cause substantial signal instability (stability conditioniv) and electrode drift, which hinders the application of SCEs forlong-term sample analysis. Such a water layer can act as a smallreservoir that can undergo ion-exchange with ions from the samplesolution contacting an ion-selective membrane. In that instance, thetransmembrane ion flux from the water layer into the sample solution candiminish the performance of the electrode in terms of detection limitsthrough the contamination of membrane/solution phase boundary. Recentexperimental reports demonstrated that ISEs containing either 3DOMcarbon or PEDOT/PSS conductive polymer as ion-to-electron transducerspossessed increased signal stability during potentiometric measurementsdue to large interfacial capacitance and high hydrophobicity of thetransducer layer. Applicants thus hypothesized that the hydrophobicityof 2D MOFs employed in this Example would inhibit the formation of waterlayer at the membrane/electrode interface, and thus minimize the effectof transmembrane ion-fluxes.

To assess the degree of water layer formation at the electrode/membraneinterface, Applicants performed contact angle measurements and carriedout a potentiometric water layer test. Contact angle measurements wereperformed by dropping 1.0 μL water aliquot onto the surface of MOFcoated glassy carbon electrode (MOF layer thickness-60 μm; membranethickness −110±10 μm). The contact angle obtained for this electrodeconfiguration was 74±0.4°, indicating substantial hydrophobicity of thestudied surface (FIG. 25 ) in contrast to unmodified glassy carbonelectrode with contact angle estimated at approximately 50°.

Even though, the observed contact angle is lower than 104° and 132°reported for CIM carbon andPEDOT-C14(tetrakis(pentafluorophenyl)borate), respectively, Applicantsanticipated that the extent of water layer formation at theelectrode/membrane interface would be minimal giving rise to high signalstability during potentiometric measurements.

A potentiometric water layer test was conducted by placing theGCE/MOF/NO₃ ⁻-ISM electrode sequentially into 0.1 M NH₄NO₃, 0.1 M CaCl₂and 0.1 M NH₄NO₃ solutions. Immediately after the primary solution wasreplaced by 0.1 M CaCl₂, a large change in the electromotive force wasobserved directly reflecting the selectivity of the electrodes (FIG.24A). The same electrode also in 0.1 M CaCl₂ showed minimal potentialdrift, indicating that the NO₃ ⁻ ions at the membrane/electrodeinterface (water layer) were not replaced to a significant extent by Cl⁻ions. After placing the electrodes back into the primary ion solution,the MOF-based devices exhibited very small potential drift,demonstrating that the extent of water layer formation was significantlyreduced for the ISEs utilizing MOF as a conductive layer in between thepolymeric membrane and solid contact. Similarly, potentiometric watertest of GCE/MOF/K⁺-ISM-II electrodes (FIG. 24B) revealed only very smallpotential drift upon changing from primary ion solution (0.1 M KCl) tointerfering ion solution (0.1 M NaCl) and back to targeted analyteindicating good ability of Ni₃HHTP₂ MOFs to minimize the extent of waterlayer formation at the electrode/ISM interface.

Example 1.18. Summary

In summary, this Example describes the first experimental demonstrationof efficient ion-to-electron transduction facilitated by conductiveMOFs. This material's property facilitates the implementation ofconductive metal-organic frameworks in potentiometric detection. Thegenerality of this approach is established by integrating severalanalogues of 2D conductive MOFs into solid-state potentiometric devices(coated with ion-selective membrane) to achieve potentiometricdetermination of K⁺ and NO₃ ⁻ ions in aqueous solutions. The sensorsexhibit optimal performance characteristics, including near-Nernstianbehavior (54.1-58.2 mV/sec), wide dynamic range (mM-nM), and good signalstability (11.1±0.5 μA/h).

Example 1.19. Additional Data Related to the Characterization of MOFs

FIGS. 3A-3C shows scanning electron microscopy and energy dispersiveX-ray spectroscopy of M₃HHTP₂ materials. FIG. 4 shows powder x-raydiffraction (pXRD) of M₃HHTP₂ MOFs. FIGS. 5A-5C, 6A-6C and 7A-7C showX-ray photoelectron spectroscopy (XPS) spectra of M₃HHTP₂ MOFs, Ni₃HHTP₂MOFs, and Cu₃HHTP₂ MOFs, respectively.

The XPS spectra confirmed the presence of O and C along with therespective metals (Co, Cu and Ni) used for the preparation of M₃HHTP₂MOFs and revealed that all materials are charge neutral, similar toother literature reports on the M₃HITP₂ MOF analogs. High-resolution XPSanalysis further demonstrated that after washing with water and acetone,no traces of the precursors were detected in the M₃HHTP₂ MOFs,indicating the absence of potentially charge-balancing counter-ions.

In the high-resolution scan of Co 2p3 regions, Applicants observed twosets of peaks with binding energies of −780 and −795 eV, which describethe 2p3/2 and 2p1/2 levels in the theoretically expected 2:1 ratio.Further deconvolution of the 2p3 region revealed the presence of fourdistinct bands: the peaks at 781.4.2 and 794.1 eV were ascribed toCo^(II), while the peaks found at 785.5 and 802.0 eV were assigned toCo^(III) (28% of Co^(I) and 72% of Co^(II), FIGS. 5A-5C). These findingsindicate mixed valency in Co₃HHTP₂ MOFs, which are in good agreementwith other studies on the cobalt based MOFs. High-resolution XPSanalysis of Cu₃HHTP₂ MOFs also showed the presence of two peaks at 932.8and 934.6 eV, which can be ascribed to Cu^(I) and Cu^(II) centers (55%of Cu^(I), and 45% of Cu^(II)), respectively, and similarly to Co₃HHTP₂MOFs, are indicative of mixed valency within the framework (FIGS.7A-7C).

The high-resolution scan of the Ni 2p region showed the presence of twopeaks with binding energies of −851 and −870 eV, were assigned to the2p3/2 and 2p1/2 levels, respectively (FIGS. 6A-6C). The lack ofcharge-balancing counterions in the Cu₃HHTP₂ and Co₃HHTP₂ MOFs indicatesthat the variation from the 2+ oxidation state of the metal iscompensated by the redox-active HHTP ligands, which are known to be ableto accommodate a wide range of redox states. High-resolution spectrum ofthe Ni 2p region revealed only a single type of Ni, further confirmingthat no extraneous Ni²⁺ ions are present within the analyzed samples.

As such species are the only possible cations that could potentiallybalance a negatively charge material, these finding are thus stronglyindicative of charge neutrality within Ni₃HHTP₂. Moreover, deconvolutedhigh resolution spectrum for 0 is revealed the presence of two differentenvironments ˜531 eV and ˜532 eV, which were assigned to C—O and C═O,respectively. These two distinct types of O are expected for a chargeneutral molecule in which the HHTP ligand can adapt semiquinone andquinone structures (FIG. 2 ).

Example 1.20. Additional Data Related to the Characterization of GCE/MOFElectrodes

FIGS. 9A-9C and 10A-10C provide data related to the interferometry ofGCE/Ni₃HHTP₂ MOF electrodes. FIGS. 11A-11C provides cyclic voltammetryof MOFs deposited on glassy carbon electrodes. Electrochemicalcapacitors can store electrical energy by the i) electrochemical doublelayer in which charge accumulates at the interface between theelectrodes and the electrolyte; or ii) through series of faradicreactions at the surface of electrode materials. Most importantly, inthe electrochemical double layer capacitors, there is no electron flowbetween the solution and the electrode, whereas the interfacial electrontransfer between the solution and the electrode, also better known aspseudocapacitance, is observed in the latter example. Therefore, thedeliberate introduction of pseudocapacitive components may providehigher capacitance and thus result in more stable potentiometricresponse.

Cycling voltammetry of M₃HHTP₂ MOFs (FIGS. 11A-11C) drop-cast onto GCErevealed the presence of one anodic peaks at 0.14 V and two cathodicredox waves at −0.02 V and −0.13 V in Ni₃HHTP₂, and two anodic peaks at−0.14 V and 0.13 V, together with two cathodic redox waves at −0.01 Vand −0.34 V indicating the presence of faradic processes in the studiedmaterials. No faradic reactions were observed for GCE/Co₃HHHTP₂electrodes, thereby supporting the hypothesis that double layer charingis the primary mechanism responsible for the large capacitance of thismaterial.

Without being bound by theory, these observed redox processes recordedfor the Ni₃HHTP₂ and Cu₃HHTP₂ could originate from: i) redox activity ofthe metal centers or/and ligand within the MOF network; ii) co-existenceof several active redox states due to the presence of defects in the MOFlattice (e.g., exposed-edges); and iii) redox active impurities that areembedded within the coordination network. PXRD and XPS data together(FIGS. 4, 5A-5C, 6A-6C, and 7A-7C), demonstrated that no metallicimpurities/external species are present within the analzyed M₃HHTP₂ MOFsand thus they are not responisble for the observed redox activity.

Therefore, without being bound by theory, Applicants hypothesize thatthe observed redox transformations are due to the redox active nature ofthe ligand, as reported for the HHTP molecular precursors, whichpartially contributes to the overall recorded capacitance through thepresence of pseudocapacitance. In the case of Cu₃HHTP₂, the presence ofreversible redox waves indicate that the capacitive response of this MOFmainly proceeds through oxidation/reduction of the MOF. In light ofthese observations, the ion-to-electron transduction process may proceedthrough i) the formation of the electrical double layer in which oneside carries charge in the form of ions, e.g., cations or anions fromthe ion-selective membrane, while the other side of the capacitor isformed by electrical charge—electrons or holes present in the solidcontact; and/or ii) reversible oxidation/reduction (doping/undoping) ofthe MOF based transducer.

In the former situation, the interfacial potential at the ion-selectivemembrane and MOF interface may be solely defined by the quantity ofcharge stored at the electrical double layer rather than by ionpartitioning or redox reactions. Therefore, Applicants anticipate that,by using highly porous materials such as M₃HHTP₂ MOFs, the interfacialcontact between the polymeric membrane and the electrode will beincreased giving rise to higher value of capacitance and thus supportthe hypothesis that singal transduction in Ni₃HHTP₂ and Co₃HHTP₂ mainlyproceeds through the formation of electrical double layer as observedfor other porous materials. This proposed transduction mechanism may beadditionally supported by the XPS and PXRD evidence that revealed chargeneutratility in M₃HHTP₂ MOFs and lack of extraneous associatedcounter-ions that could potentially participate in the ion-to-electrontransduction process through the oxidation/reduction of the MOF basedtransducer. Likewise, the second transduction mechanism may be dominantin the Cu₃HHTP₂ MOFs in which reversible redox reaction of the MOF filmwould ensure stable interfacial potential.

FIG. 12 shows the electrochemical impedance spectroscopy of GCE/Ni₃HHTP₂MOF at different applied potentials. FIGS. 21A-21C show potentiometricresponses obtained for the ISEs containing M₃HHTP₂ MOFs as theunderlying conductive layer. FIG. 16 shows potentiometric slopesobtained for various cations and anions during selectivity measurementsof potassium and nitrate selective electrodes.

FIGS. 22-23 show selectivity coefficients and experimental slopesobtained for K⁺ and NO₃-ISEs. FIG. 17 shows short-term stabilitymeasurement of NO₃ ⁻-ISM electrodes with drop-cast layer of Ni₃HHTP₂MOFs. FIG. 18 shows the long-term stability measurement of NO₃ ⁻-ISMElectrodes with drop-cast layer of Ni₃HHTP₂ MOF.

FIG. 19 shows light stability of K⁺-ISM-II electrodes with drop-castlayer of Ni₃HHTP₂ MOF. FIG. 20 shows powder X-ray diffraction (pXRD) ofM₃HHTP₂ MOFs after potentiometric measurements. FIG. 25 shows contactangle of water on the surface of Ni₃HHTP₂ coated electrodes.

Example 2. Conductive Metal-Organic Frameworks as Ion-SelectiveElectrodes in Potentiometric Measurements

This Example demonstrates the implementation of conductive M₃HHTP₂ MOFsas both ion recognition centers and ion-to-electron transducers inpotentiometric sensing. In particular, this Example features theintegration of 2D conductive MOFs that includes of nickel and coppermetal centers interjoined with 2,3,6,7,10,11-hexahydroxytriphenyleneorganic units organized into a Kagome lattice. These materials exhibitoptimal electrical conductivity—0.2 S/cm as reported for Cu₃HHTP₂ MOFand can act as signal transducers in ISEs. However, their ability tosimultaneously detect ions and transduce the response from ions intoelectrons has not been yet demonstrated.

Applicants focus on the use of Cu₃HHTP₂ MOFs and Ni₃HHTP₂ MOFs as modelsystems in the fabrication of one-component ion-selective sensors. Forthis purpose, Applicants integrated the MOFs into a single-pieceelectrodes by compressing the MOF powder directly onto the customizedgold electrodes (FIG. 26 ). In this configuration, the resulting ISEsexhibited near-Nernstian behavior to a range of cationic and anionicanalytes. Moreover, these materials show good potential stability,minimal photosensitivity and limited sensitivity to atmospheric gases.

Example 2.1. Materials

All metal salts were of analytical reagent grade and purchased fromSigma Aldrich. Solutions of metal ions were prepared in ultra-pure waterobtained with Pico Pure 3 water system (resistance 18 MΩ cm⁻¹). Workingsolutions of different metal ions were prepared by serial dilutions of a1 M stock solution. Customized gold electrodes (3 mm in diameter) withhollow opening (3 mm in depth) were fabricated at Dartmouth College.

Example 2.2. Synthesis of Conductive MOFs

The synthesis of 2D conductive metal-organic frameworks using organiclinker 2,3,6,7,10,11-hexahydroxytriphenylene was adapted from a priorstudy (Chem. Mater. 2016, 28, 5989-5998). Briefly, to a 100 mL roundbottom flask, 500 mg of HHTP and 767 mg of Ni(OAc)₂.4H₂O were added. 70mL of deionized water was then added to the round bottom flask. Theresulting suspension was sonicated for 15 minutes. The reaction mixturewas then heated for 24 h at 85° C. under stirring. The flask was left tocool for 1 h at room temperature and the reaction product was filteredwith a ceramic funnel and a filter paper. The solid precipitate was thenwashed with ultra-pure water (1000 mL) and acetone (300 mL). Theresulting black powder was transferred into a glass vial and driedovernight under vacuum (20 mTorr) at 85° C.

Example 2.3. Preparation of MOF-Based ISEs

For all electrochemical measurements, 10 mg of MOF powder was compressedfor 1 h at 6900 Nm⁻² directly on the top of customized gold electrode.If not otherwise state the resulting electrodes were placed directly inthe solution used for the potentiometric measurements without any priorconditioning.

Example 2.4. Potentiometric Measurements

Potentiometric measurements were performed using EmStat MUX16potentiostat (Palm Instruments BV, Netherlands) at room temperature in astirred solution against a double-junction Ag/AgCl reference electrodewith a 1 M KCl bridge electrolyte (Sigma Aldrich).

Example 2.5. Ion-Exchange Properties of Ni₃HHTP₂ and Cu₃HHTP₂ MOFPressed Electrodes

The analytical applicability of the fabricated Cu₃HHTP₂ electrodes indirect potentiometric sensing of ionic species in solutions was assessedby measuring the EMF response in the presence of various cationic andanionic analytes. Applicants used the electrode configuration in whichthe conductive MOF was firstly pressed onto the top of a gold contactand then immersed in the sample solution directly without any electrodepretreatment (e.g. application of ion-selective membrane orconditioning).

The first step of this Example was to investigate if either of theCu₃HHTP₂ or Ni₃HHTP₂ MOFs exhibits ion-exchange properties. As it can beseen in FIG. 27 , upon varying concentrations of Na⁺ and Cl⁻ ions in thesample, Cu₃HHTP₂ based electrodes showed near-Nernstian response to K⁺,ions while Ni₃HHTP₂ electrodes exhibited substantially sub-Nernstianresponse to Cl⁻. As the metal-HHTP complexes are known to undergoreversible transformations between the catechol, semiquinone and quinoneredox forms, the differences in the type of potentiometric signalrecorded for both materials are likely to be attributed to varyingoxidation states of each HHTP-based MOF. In the case of Cu₃HHTP₂, theobserved cationic response indicates that this material is most likelyto be present in its reduced form and thus have positively chargedcounter-ions to stabilize the overall charge on the molecule. Theassociated ions can then be exchanged by other cations giving rise toion-exchange properties.

Without being bound by theory, Applicants hypothesize that a similarmechanism applies to Ni₃HHTP₂ MOF pressed electrodes. However, theobserved anionic response may be due to the presence of exchangeablenegatively charged ions associated with the Ni₃HHTP₂ material. The totalamount of counter-ions introduced during the synthesis and consequentlypresent in each studied MOF could not be yet quantified. Nonetheless,the observed ion-exchange properties highlight the potential of M₃HHTP₂MOFs as direct potentiometric sensors.

Example 2.6. Potentiometric Response of Cu₃HHTP₂ Electrodes

The ionic responses of Cu₃HHTP₂ MOF pressed electrodes were testedagainst a number of cationic species (Cu²⁺, Ni²⁺, co²⁺, Pb²⁺, Zn²⁺,Ca^(2±), Mg²⁺, K⁺, Na⁺, and NH⁴⁺) using standard addition methods (Table4).

TABLE 4 Potentiometric responses of Ni₃HHTP₂ pressed electrodes tovarious anionic species. Ion Linear response range [M] Slope [mV/decade]Ca²⁺ 3 × 10⁻⁴-2 × 10⁻² 32.9 ± 0.7 Co²⁺ 3 × 10⁻⁴-6 × 10⁻³ 31.3 ± 1.3 Mg²⁺1 × 10⁻³-6 × 10⁻³ 18.0 ± 2.3 Zn²⁺ 1 × 10⁻³-6 × 10⁻³ 22.1 ± 1.1 Pb²⁺ 3 ×10⁻⁴-3 × 10⁻² 34.1 ± 0.8 Ni²⁺ 1 × 10⁻³-3 × 10⁻² 31.2 ± 1.2 Cu²⁺ 3 ×10⁻⁴-2 × 10⁻² 31.9 ± 0.6 Na⁺ 1 × 10⁻⁴-2 × 10⁻² 47.3 ± 1.4 K⁺ 1 × 10⁻⁴-2× 10⁻² 49.2 ± 0.9 NH₄ ⁺ 1 × 10⁻³-2 × 10⁻² 51.5 ± 2.3

On each occasion, an increase in the recorded electromotive force (EMF)was observed, confirming the cationic response mechanism of the Cu₃HHTP₂electrodes. Regardless of the order of the electrolyte used for themeasurements, the electrodes responded in the near-Nernstian fashion toall tested analytes. In traditional polymer based ISEs, such behaviormay indicate that the ionophore acts as a non-specific ion-exchangerwith selectivity pattern often following the Hofmeister selectivityorder. However, in the case of Cu₃HHTP₂ electrodes, a large potentialjump (73.4 mV) was observed upon the addition of Cu²+ ions into thesample solution.

Without being bound by theory, Applicants hypothesize that theoccurrence of this super-Nernstian response may directly reflectselectivity of the Cu₃HHTP₂ MOF pressed electrodes. As the electrodecomes in contact with the ion to which it is more selective, theMOF-associated counter ion would be replaced by the primary ion, thusinducing an abnormally high increase in potential (bulk ion-exchange).Without being bound by theory, increased selectivity of Cu₃HHTP₂ MOF tocopper ions may be due to: i) preferential electrostatic interactions ofCu²⁺ with oxygen atoms embedded within the MOF network; ii) interactionsbetween axially coordinated ligand (e.g. coordinated water) and targetedmetal; iii) electrostatic interactions between the exposed edges of theMOF lattice (—OH groups) with copper ions; and iv) combined interactionsincluding electrostatic, size exclusion, and metal-hydrogen bonding.

Example 2.7. Ionic Responses of Ni₃HHTP₂ Pressed Electrodes

To further demonstrate the applicability of MOFs in the anion detection,Applicants prepared fresh Ni₃HHTP₂ MOF pressed electrodes and thenevaluated their response. Upon the initial exposure of Ni₃HHTP₂ MOF toNa⁺ and Cl⁻ ions, the electrodes showed sub-Nernstian response(−24.9±1.1 mV/decade) to chloride in the concentration range spanningfrom 1×10⁻⁴ M to M to 1×10⁻² M (FIG. 29 ). At the concentrationsexceeding 1×10⁻² M of chloride in the solution, the electrodes stoppedresponding to the primary ions, indicating that upper detection limitsof the Ni₃HHTP₂ MOF were reached. At higher concentrations of chloride,the recorded potentiometric response became inverted and the electrodesstarted responding primarily to cations.

The reversal of potentiometric response is not uncommon for polymerbased ion-selective electrodes when the concentration of free analyte inthe membrane exceeds the one dictated by the presence of ionophore. Inthis situation, the diffusion of primary ion into the membrane isaccompanied by the co-extraction of the counter-ion from the sampleresulting in Donnan exclusion failure. Furthermore, depending on thenature of the polymeric membrane (e.g. polarity, type of dissolvedsensing components), various ion-pairing events may occur (ion-pairformation between ionic sites and primary ions) producing, for instance,a cationic response to anions in the solution. In the case of Ni₃HHTP₂MOF, Applicants can hypothesize that at a high concentration of theelectrolyte, Cl⁻ can be axially-coordinated to Ni in the MOF network,facilitating the formation of ‘ion-pairs’, and thus producing a cationicresponse.

Applicants also tested the response of Ni₃HHTP₂ MOF to a range ofanionic species (Table 5). Interestingly, the electrodes exhibited onlylimited response (sub-Nernstian) to anions with the exception of NO₃ ⁻to which Ni₃HHTP₂ MOF showed near-Nernstian (−48.2±1.4 mV/decade)behavior over a satisfactory response range. This surprisingly limitedresponse to anions may be caused by i) high selectivity of the Ni₃HHTP₂MOF to the associated counter-ions as if the targeted analyte cannotcompletely displace the complexed counter-ions from the phase boundaryregion of the electrode, and a sub-Nernstian response would be expected;ii) the electrode exhibits mixed selectivity to cations and anions, andthe response characteristics for a specific ion would be dictated by thetype of ions used in the measurements; iii) ionic impurities presentwithin the MOF network may produce a partial response to cations, thusdiminishing the magnitude of anionic response; and iv) metal-ionspecific interactions (metal in the MOF network acts as either Bronstedor Lewis acid) that are depended on the type of ions present in thesolution (axially coordinated ligands such as water or chloride).

TABLE 5 Potentiometric responses of Ni₃HHTP₂ pressed electrodes tovarious anionic species. Ion Linear response range [M] Slope [mV/decade]CH₃COO⁻ No response N/A NO₃ ⁻ 3 × 10⁻⁴-6 × 10⁻³ −48.2 ± 1.4 ClO₄ ⁻ 1 ×10⁻³-6 × 10⁻³  33.4 ± 3.1 Cl⁻ 1 × 10⁻³-6 × 10⁻³ −24.9 ± 1.1 I⁻ Noresponse N/A F⁻ No response N/A SO₄ ²⁻ 1 × 10⁻³-6 × 10⁻³  −7.6 ± 2.0S₂O₈ ²⁻ No response N/A Cr₂O₇ ²⁻ No response N/A

Example 2.8. Effect of Ambient Light on the Stability ofSingle-Component MOF Based Electrodes

Solid contact electrodes can be photosensitive if the transducing layer(e.g. organic semiconductor) at the solid contact/polymeric membraneinterface has a sufficient band gap to excite electrons from the valenceband into the conduction bands. This process may result in thephotooxidation of the material consequently leading to significantpotential instability as reported for ISEs based on conductive polymers.To assess light sensitivity, Cu₃HHTP₂ and Ni₃HHTP₂ MOFs were pressedinto the electrodes and immersed in the 10 mM CuSO₄ solution. During theexperiments, the electrochemical cell was firstly exposed to ambientlight for 1 h and then kept in the dark (3 h) until the electrodes wereilluminated again with ambient light for 1 h. As shown in FIG. 30 , nosignificant potential shifts were observed indicating that M₃HHTP₂ MOFsare insensitive to light.

Example 2.9. Influence of Oxygen on Potential Stability of Cu₃HHTP₂Pressed Electrodes

Applicants also studied the effect of oxygen on the potential stabilityof Cu₃HHTP₂ and Ni₃HHTP₂ MOFs electrodes. In conventional potentiometricsolid-state ion-selective electrodes, oxygen may diffuse through thepolymeric membrane to form an O₂ half-cell at the surface of the solidcontact. As a result, substantial potential/signal instability may beencountered, precluding the application of ISEs as robust analyticaldevices. In this study, oxygen interference on the response of pressedelectrodes to Cu²⁺ ions was studied by immersing each electrode in 10 mMCuSO₄ solution while repeatedly bubbling oxygen and nitrogen through thesample. As demonstrated in FIG. 31 , only a small change in the recordedpotential is observed upon exposure of Cu₃HHTP₂ and Ni₃HHTP₂MOFs to N₂and O₂. This remarkable potential stability exceeds (100 times higherthan for polypyrrole based ISEs) or is on par with those reported fornanoporous carbons.

Example 2.10. Chemicals and Solvents

All chemicals and solvents were purchased from Sigma Aldrich, TCI,Fisher, or Alfa Aesar and used as received. Scanning Electron Microscopy(SEM) and Energy Dispersive X-ray Spectroscopy (EDX) was performed usinga Hitachi TM3000 SEM (Tokyo, Japan) equipped for X-ray microanalysiswith a Bruker Edax light element Si(Li) detector (Billerica, Mass.).EmStat MUX16 potentiostat (Palm Instruments BV, Netherlands) was usedfor electrochemistry. The z-dimension (height) for all electrodes werecollected using a Zygo NewView 7300 Light Interferometer equipped with a10× lens.

Example 2.11. Synthesis of Cu₃HHTP₂ MOFs

To a 50 mL round bottom flask, 100 mg of HHTP and 154 mg of CuSO₄.5H₂Owere added. 20 mL of deionized water was then added to the round bottomflask. The resulting suspension was sonicated for 15 minutes. Thereaction mixture was then heated for 24 h at 70° C. under stirring. Theflask was left to cool for 1 h at room temperature and the reactionproduct was filtered with a ceramic funnel and a filter paper. The solidprecipitate was then washed with ultra-pure wate water (1000 mL) andacetone (300 mL). The resulting black powder was transferred into aglass vial and dried overnight under vacuum (20 mTorr) at 85° C.

Example 2.12. Synthesis of Co₃HHTP₂MOFs

To a 50 mL round bottom flask 50 mg of HHTP and 74 mg of CoCl₂.6H₂O wereadded. 20 mL of deionized water was then added to the round bottomflask. The resulting suspension was sonicated for 15 minutes. Thereaction mixture was then heated for 24 h at 70° C. under stirring. Theflask was left to cool for 1 h at room temperature and the reactionproduct was filtered with a ceramic funnel and a filter paper. The solidprecipitate was then washed with ultra-pure wate water (1000 mL) andacetone (300 mL). The resulting black powder was transferred into aglass vial and dried overnight under vacuum (20 mTorr) at 85° C.

Example 2.13. Choice of Materials

Applicants chose a class of modular MOFs that includes of metal centers(M=Cu, Ni) interconnected with —OH triphenylene ligands to fabricatesingle-piece ion-selective electrodes. This class of 2D dimensionalmaterials deems appropriate for the applied investigation of ion-bindingproperties for at least six reasons: i) M₃HHTP₂ can be synthesizedthrough bottom-up self-assembly from modular commercially availablemolecular building blocks (FIG. 32 ). This approach permits theinvestigation of the role of the metal center (e.g., Ni, Cu) and therole of the chalcogen atom in the ion-binding event; ii) The pore sizeof 2 nm in diameter in the synthesized MOFs is suitable for the rapiddiffusion of small ionic species; iii) M₃HHTP₂ MOFs can transduce ionicsignal into electronic output; iv) The MOFs implemented herein havelarge bulk capacitance, thus ensure sufficient signal stability inpotentiometric measurements; v) Inherent conductivity of these materialsenables their implementation as electrical components; and vi) Thesematerials can be effectively compressed without the substantial loss ofstructural integrity, therefore allowing their implementation intodevices.

Example 2.14. Electrochemical Measurements

Applicants chose to use potentiometry for characterizing the ability ofMOFs pressed electrodes to interact with ions in the aqueous solution.This technique enables the fundamental investigation of ion-MOF specificinteractions and permits the assessment of signal stability underdifferent environmental conditions (e.g., photosensitivity, sensitivityto gaseous compounds). Applicants reasoned that compressing M₃HHTP₂ MOFsonto a gold customized electrodes will result in a robust electricalcontact capable of withstanding long-term sample analysis in aqueoussolutions.

Applicants adopted a common two electrode set-up with customized goldelectrodes, and double junction Ag/AgCl reference electrode for allpotentiometric measurements. As the measured potential is a directfunction of the activity of ions in the investigated sample (Nernstiansystem), it allows both qualitative and quantitative analysis of speciesin the solution.

Example 2.15. Device Design

For the potentiometric determination of ionic species in aqueoussolutions, Applicants integrated M₃HHTP₂ MOFs by compressing 10 mg ofeach material directly on the top of custom-made gold electrodes. Eachelectrode included of PVC body and a gold contact (3 mm in diameter)soldered to the copper wire. The gold contact was machined into the bodyof the electrode leaving a 3×3 mm cavity for powder loading. Applicantsused a hydraulic press to compress the MOF, within the produced cavity,directly onto the gold contact (1 h at 6900 Nm⁻²). In each device,Applicants utilized PVC body to establish a protective barrier betweenthe electrical components and surrounding solution.

Applicants also used copper wiring and gold conductive substrate toestablish an electrical contact between the MOF and the power supply.The use of these materials is highly advantageous for the proposeddevice architecture due to: i) optimal electrical conductivity; ii)widespread commercial availability, iii) compatibility with manyelectrical components; iv) low cost; and v) high resistivity tocorrosion and dissolution of gold and PVC in aqueous solutions.

In this configuration (FIG. 26 ), the MOF is integrated onto the top ofunderlying gold substrate and it is directly in contact with the aqueoussolution. Applicants reasoned that any changes in the activity of ionsin the solution will be simultaneously recognized and transduced intoelectronic signal by the metal-organic frameworks and then directlyrecorded by the potentiostat.

Scanning electron microscopy and energy dispersive X-ray spectroscopy ofMe₃HHTP₂ MOFs are shown in FIGS. 33A-33C. Upper detection limits ofNi₃HHTP₂ MOF pressed electrodes are illustrated in FIG. 29 .

Example 3. Scavenging of Toxic Ions from Aqueous Media Using LayeredTwo-Dimensional Metal-Organic Frameworks

This Example demonstrates the multifunctional ability of a family ofconductive two-dimensional (2D) metal—organic frameworks (MOFs) toremove Cr(VI) and Mn(VII) from aqueous solutions. These MOFs arecomprised of metallic nodes interconnected via hexatopictriphenylene-based organic ligands(2,3,6,7,10,11-hexahydroxytriphenylene, HHTP, and2,3,6,7,10,11-hexaiminotriphenylene, HITP). Ion capture study involvingUV vis spectroscopy and inductively coupled plasma mass spectroscopy(ICP-MS) shows promising capacity of these MOFs for metal ions.Additionally, the structural integrity of the MOFs is confirmed usingpowder X-ray diffraction (pXRD). Coupling ion filtration studies withchemical detection suggests promising multifunctional properties ofthese materials for simultaneous sensing, capture, and filtration oftoxic metal ions.

FIG. 34 illustrates an experimental setup for the capture of ions by aMOF-based ion capture membrane. FIG. 35 provides simulated andexperimental PXRD patterns of Cu₃(HHTP)₂, Cu₃(HITP)₂, Ni₃(HITP)₂ andNi₃(HHTP)₂ MOFs. FIGS. 36A-D provide depictions of the structures ofNi₃(HHTP)₂ (FIG. 36A), Ni₃(HITP)₂ (FIG. 36B), Cu₃(HHTP)₂ (FIG. 36C), andCu₃(HITP)₂ (FIG. 36D) MOFs. FIGS. 37A-D provide SEM images of Ni₃(HHTP)₂(FIG. 37A), Ni₃(HITP)₂ (FIG. 37B), Cu₃(HHTP)₂ (FIG. 37C), and Cu₃(HITP)₂(FIG. 37D) MOFs.

FIGS. 38A-B provide experimental results of the capture of dichromate(Cr₂O₇)²⁻ (FIG. 38A) and Permanganate (MnO₄)⁻ (FIG. 38B) by variousMOFs. In brief, 5 mg of K₂Cr₂O₇/KMnO₄ was dissolved in 5 mL H₂O (1000ppm solution). Thereafter, 5 mg of MOF was added to this solution. Theresulting mixture was then stirred (240 rpm) at room temperature for 24hours. After 24 hours, stirring was stopped and the mixture was allowedto settle down. Next, a small amount of solution was taken out from thismixture cautiously with a pipette. This solution was then analyzedfurther via ICP-MS.

FIGS. 39A-B illustrate the concentration dependent ion capture ofdichromate (FIG. 39A) and permanganate (FIG. 39B) ions by Ni₃(HITP)₂MOFs. FIGS. 40A-B illustrate time dependent ion capture of dichromate(FIG. 40A) and permanganate (FIG. 40B) ions by Ni₃(HITP)₂ MOFs. Thecapture of dichromate and permanganate ions by Ni₃(HITP)₂ MOFs weremonitored over time using UV Vis. spectroscopy.

FIGS. 41A-B illustrate time dependent ion capture of dichromate (FIG.41A) and permanganate (FIG. 41B) ions by Ni₃(HITP)₂ MOFs. The capture ofdichromate and permanganate ions by Ni₃(HITP)₂ MOFs were monitored overtime using inductively coupled plasma mass spectroscopy (ICP-MS). FIGS.42A-B show post ion-capture characterization of Ni₃(HITP)₂ MOFs by pXRDafter the capture of dichromate (FIG. 42A) and permanganate (FIG. 42B)ions.

FIG. 43 illustrates the potentiometric sensing of KMnO₄ with Ni₃(HITP)₂.Illustrated is the potentiometric response of Ni₃(HITP)₂ electrodes todilute (i.e., 50 nM-10 μM) KMnO₄. The electrolyte used was 0.1 M KCl.The working electrodes were fabricated by drop casting 2-2.5 μL drops ofa 2 mg/mL MOF suspension onto glassy carbon electrodes. The counterelectrodes included platinum wires (i.e., Ag/AgCl).

In case of glassy carbon electrodes without MOFs, Applicant observedthat the V increased with each addition of permanganate ion in the cell(triangular dots in FIG. 43 ), which is due to an increase in theelectrolyte concentration. However, in the case of MOF modifiedelectrodes, Applicant observed a significantly lower change (square dotsin FIG. 43 ), which can be attributed to adsorption of permanganate ionson the MOFs.

In sum, four triphenylene based MOFs, namely Cu₃(HHTP)₂, Cu₃(HITP)₂,Ni₃(HHTP)₂ and Ni₃(HITP)₂, were synthesized. These MOFs were thencharacterized by pXRD and SEM. Ion capture experiments for dichromateand permanganate ions were then carried out with these MOFs. Withoutbeing bound by theory, Applicant envisions that the presence of openmetal sites in the framework can act as anchoring sites for oxo-ionspresent in the aqueous media. At the same time, the electronicallyconductive nature of the MOFs can allow electrochemical sensing of theseoxo-ions.

Ni₃(HITP)₂ MOF showed better ion adsorption when compared to other MOFs.In particular, Ni₃(HITP)₂ MOFs were able to remove 99.99% ofpermanganate ions and 80% of dichromate ions from a 1000 ppm solution ofrespective ions.

Time dependent and concentration dependent capture of permanganate anddichromate ions were also performed with Ni₃(HITP)₂ MOFs. Additionally,potentiometric sensing for permanganate ions was carried out withNi₃(HITP)₂ MOFs.

Superior ion capture results are observed when the ion capturecapacities of Ni₃(HITP)₂ are compared with other materials. Inparticular, Applicant observed dichromate and permanganate capturecapacities of 801 mg/g and 999 mg/g for Ni₃(HITP)₂. On the other hand,prior permanganate capture capacities of MOFs only amounted to 283 and297 mg/g. Chem. Sci., 2018, 9, 7874-7881 and J. Am. Chem. Soc. 2010,132, 20, 7202-7209.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present disclosure to itsfullest extent. The embodiments described herein are to be construed asillustrative and not as constraining the remainder of the disclosure inany way whatsoever. While the embodiments have been shown and described,many variations and modifications thereof can be made by one skilled inthe art without departing from the spirit and teachings of theinvention. Accordingly, the scope of protection is not limited by thedescription set out above, but is only limited by the claims, includingall equivalents of the subject matter of the claims. The disclosures ofall patents, patent applications and publications cited herein arehereby incorporated herein by reference, to the extent that they provideprocedural or other details consistent with and supplementary to thoseset forth herein.

What is claimed is:
 1. A method of capturing one or more ions from anenvironment, said method comprising: associating the environment with acomposition comprising a metal-organic framework, wherein themetal-organic framework comprises a plurality of metals and a pluralityof aromatic ligands coordinated with the plurality of metals, whereinthe plurality of metals comprise metals with open metal sites, whereinthe plurality of the aromatic ligands comprise a plurality of functionalgroups coupled to the aromatic ligands, wherein the functional groupsare operational to interact with the one or more ions, and wherein theassociating results in the capturing of the one or more ions by themetal-organic framework.
 2. The method of claim 1, wherein themetal-organic framework is in the form of a multi-layered and stackedstructure.
 3. The method of claim 1, wherein the metal-organic frameworkis in the form of a two-dimensional conductive network, and wherein themetal-organic framework is in crystalline form.
 4. The method of claim1, wherein the plurality of metals are selected from the groupconsisting of nickel, copper, and combinations thereof.
 5. The method ofclaim 1, wherein the plurality of aromatic ligands comprise a pluralityof hexatopic ligands.
 6. The method of claim 1, wherein the plurality ofaromatic ligands comprise a plurality of polycyclic aromatic ligands. 7.The method of claim 6, wherein the plurality of polycyclic aromaticligands comprise a plurality of connected aromatic rings.
 8. The methodof claim 6, wherein the plurality of polycyclic aromatic ligandscomprise a plurality of triphenylene-based ligands.
 9. The method ofclaim 8, wherein the plurality of the triphenylene-based ligands areselected from the group consisting of hexatopic triphenylene-basedligands, 2,3,5,6,10,11-hexahydroxytriphenylene (HHTP),2,3,5,6,10,11-hexaiminotriphenylene (HITP),2,3,5,6,10,11-hexathiotriphenylene (HTTP), and combinations thereof. 10.The method of claim 1, wherein the plurality of functional groups areselected from the group consisting of hydroxy groups, amine groups,thiol groups, coordinated groups thereof, deprotonated groups therefore,and combinations thereof.
 11. The method of claim 1, wherein themetal-organic framework is selected from the group consisting ofNi₃(HHTP)₂, Ni₃(HITP)₂, CU₃(HHTP)₂, Cu₃(HITP)₂, and combinationsthereof.
 12. The method of claim 1, wherein the metal-organic frameworkcomprises Ni₃(HITP)₂.
 13. The method of claim 1, wherein the one or moreions comprises one or more cations selected from the group consisting ofCa²⁺, Co²⁺, Mg²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Cu²⁺, Na⁺, K⁺, NH₄ ⁺, Hg²⁺, andcombinations thereof.
 14. The method of claim 1, wherein the one or moreions comprises one or more anions selected from the group consisting ofCH₃COO⁻, MNO₄ ⁻, NO₃ ⁻, ClO₄ ⁻, Cl⁻, I⁻, F⁻, Br⁻, SO₄ ²⁻, S₂O₈ ²⁻, Cr₂O₇²⁻, and combinations thereof.
 15. The method of claim 1, wherein the oneor more ions comprises MNO₄ ⁻, Cr₂O₇ ²⁻, or combinations thereof. 16.The method of claim 1, wherein the environment is in a gaseous form, aliquid form, a solid form, or combinations of such forms.
 17. The methodof claim 1, wherein the environment is in liquid form.
 18. The method ofclaim 1, wherein the associating results in the selective association ofone or more specific ions in the environment with the metal-organicframework.
 19. The method of claim 1, wherein the metal-organicframework comprises an ion capture capacity of more than 300 mg of ionper g of metal-organic framework.
 20. The method of claim 1, furthercomprising a step of detecting the one or more captured ions.
 21. Themethod of claim 20, wherein the detecting comprises detecting a changein potential of the metal-organic framework, and correlating the changein the potential to the presence of the one or more ions.
 22. The methodof claim 1, wherein the metal-organic framework is a component of anion-selective electrode, wherein the ion-selective electrode comprisesthe metal-organic framework and an electrode surface, wherein themetal-organic framework is associated with the electrode surface in amanner that forms an interface between the metal-organic framework andthe electrode surface, and wherein the metal-organic framework mediatesion-to-electron transduction through the interface.
 23. A compositionfor capturing one or more ions from an environment, said compositioncomprising: a metal-organic framework, wherein the metal-organicframework comprises a plurality of metals and a plurality of aromaticligands coordinated with the plurality of metals, wherein the pluralityof metals comprise metals with open metal sites, wherein the pluralityof the aromatic ligands comprise a plurality of functional groupscoupled to the aromatic ligands, and wherein the functional groups areoperational to interact with the one or more ions; and wherein thecomposition is in the form of a membrane.
 24. The composition of claim23, wherein the plurality of aromatic ligands comprise a plurality ofhexatopic ligands.
 25. The composition of claim 23, wherein theplurality of aromatic ligands comprise a plurality of polycyclicaromatic ligands.
 26. The composition of claim 25, wherein the pluralityof polycyclic aromatic ligands comprise a plurality of connectedaromatic rings.
 27. The composition of claim 25, wherein the pluralityof polycyclic aromatic ligands comprise a plurality oftriphenylene-based ligands.
 28. The composition of claim 27, wherein theplurality of the triphenylene-based ligands are selected from the groupconsisting of hexatopic triphenylene-based ligands,2,3,5,6,10,11-hexahydroxytriphenylene (HHTP),2,3,5,6,10,11-hexaiminotriphenylene (HITP),2,3,5,6,10,11-hexathiotriphenylene (HTTP), and combinations thereof. 29.The composition of claim 23, wherein the plurality of functional groupsare selected from the group consisting of hydroxy groups, amine groups,thiol groups, coordinated groups thereof, deprotonated groups therefore,and combinations thereof.
 30. The composition of claim 23, wherein themetal-organic framework is selected from the group consisting ofNi₃(HHTP)₂, Ni₃(HITP)₂, Cu₃(HHTP)₂, Cu₃(HITP)₂, and combinationsthereof.
 31. The composition of claim 23, wherein the metal-organicframework comprises Ni₃(HITP)₂.